JP6035883B2 - Method for measuring the remaining capacity of a lithium ion battery - Google Patents
Method for measuring the remaining capacity of a lithium ion battery Download PDFInfo
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- JP6035883B2 JP6035883B2 JP2012126970A JP2012126970A JP6035883B2 JP 6035883 B2 JP6035883 B2 JP 6035883B2 JP 2012126970 A JP2012126970 A JP 2012126970A JP 2012126970 A JP2012126970 A JP 2012126970A JP 6035883 B2 JP6035883 B2 JP 6035883B2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 132
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 132
- 238000000034 method Methods 0.000 title claims description 50
- 238000007600 charging Methods 0.000 claims description 44
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 22
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- -1 for example Substances 0.000 description 15
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910010043 Li1.20Mn0.40Fe0.20Ni0.20O2.00 Inorganic materials 0.000 description 1
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- 229910010352 Li1.26Mn0.52Ni0.22O2.00 Inorganic materials 0.000 description 1
- 229910010349 Li1.26Mn0.63Ni0.11O2.00 Inorganic materials 0.000 description 1
- 229910010404 Li1.29Mn0.57Fe0.07Ni0.14O2.00 Inorganic materials 0.000 description 1
- 229910010402 Li1.29Mn0.57Ni0.14O2.00 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 150000002642 lithium compounds Chemical class 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Tests Of Electric Status Of Batteries (AREA)
- Charge And Discharge Circuits For Batteries Or The Like (AREA)
Description
本実施形態は、リチウムイオン電池の残存容量の測定方法に関する。 The present embodiment relates to a method for measuring the remaining capacity of a lithium ion battery.
層状岩塩型構造を有するリチウム酸化物を主成分とする正極と、リチウムイオンを吸蔵放出可能な材料を主成分とする負極とを備えるリチウムイオン電池は、高エネルギー密度の二次電池として期待されている。 A lithium ion battery comprising a positive electrode mainly composed of lithium oxide having a layered rock salt structure and a negative electrode mainly composed of a material capable of occluding and releasing lithium ions is expected as a secondary battery having a high energy density. Yes.
しかしながら、前記リチウムイオン電池の充放電曲線には大きなヒステリシスが生じる場合がある。充放電曲線にヒステリシスが存在する場合、リチウムイオン電池の残存容量を開放起電力から推定できない課題がある。 However, a large hysteresis may occur in the charge / discharge curve of the lithium ion battery. When hysteresis exists in the charge / discharge curve, there is a problem that the remaining capacity of the lithium ion battery cannot be estimated from the open electromotive force.
特許文献１には、リチウムイオン電池の開放起電力から残存容量を測定する方法が開示されている。特許文献２及び３には、開放起電力から残存容量を推定する方法と、充放電電流を積算して残存容量を測定する方法とのハイブリッド化によって、正確な残存容量を測定する演算装置が開示されている。 Patent Document 1 discloses a method for measuring a remaining capacity from an open electromotive force of a lithium ion battery. Patent Documents 2 and 3 disclose an arithmetic device that accurately measures the remaining capacity by hybridizing a method for estimating the remaining capacity from the open electromotive force and a method for measuring the remaining capacity by integrating the charge / discharge current. Has been.
しかしながら、特許文献１に記載の方法では、ヒステリシスの大きな充放電曲線を示すリチウムイオン電池において、正確な残存容量を測定することができない。また、特許文献２及び３に記載の演算装置を用いれば、ヒステリシスの大きなリチウムイオン電池においても比較的正確に残存容量を測定することができるが、残存容量を測定するための演算装置が大掛かりになる課題がある。 However, the method described in Patent Document 1 cannot accurately measure the remaining capacity in a lithium ion battery exhibiting a large charge / discharge curve with high hysteresis. In addition, if the arithmetic devices described in Patent Documents 2 and 3 are used, the remaining capacity can be measured relatively accurately even in a lithium ion battery having a large hysteresis, but the arithmetic device for measuring the remaining capacity is large. There is a problem.
本実施形態は、開放起電力から簡単かつ正確に残存容量を測定できる方法を提供することを目的とする。 An object of the present embodiment is to provide a method capable of easily and accurately measuring a remaining capacity from an open electromotive force.
本実施形態に係るリチウムイオン電池の残存容量の測定方法は、層状岩塩型構造を有する、下記式（１）
ＬｉｘＭ１ ｙＭ２ ｚＯ２−ｄ （１）
（前記式（１）において、１．１６≦ｘ≦１．３２、０．３３≦ｙ≦０．６３、０．０６≦ｚ≦０．３１及び０≦ｄ≦０．２０である。Ｍ１はＭｎ、Ｔｉ及びＺｒからなる群から選択される少なくとも一種、Ｍ２はＦｅ、Ｃｏ、Ｎｉ及びＭｎからなる群から選択される少なくとも一種である。）
で示されるリチウム酸化物を含む正極と、リチウムイオンを吸蔵放出可能な材料を含む負極とを備えるリチウムイオン電池の残存容量の測定方法であって、
リチウムイオン電池を充電する工程と、
充電されたリチウムイオン電池について、電池全容量の０．１％以上を一部放電する工程と、
一部放電されたリチウムイオン電池の開放起電力を測定する工程と、
前記開放起電力から残存容量を算出する工程と、
を含む。
The method for measuring the remaining capacity of a lithium ion battery according to the present embodiment has a layered rock salt structure and has the following formula (1).
Li x M 1 y M 2 z O 2-d (1)
(In the formula (1), 1.16 ≦ x ≦ 1.32, 0.33 ≦ y ≦ 0.63, 0.06 ≦ z ≦ 0.31 and 0 ≦ d ≦ 0.20. M 1 the Mn, at least one selected from the group consisting of Ti and Zr, M 2 is at least one selected from the group consisting of Fe, Co, Ni and Mn.)
A method for measuring the remaining capacity of a lithium ion battery comprising a positive electrode containing lithium oxide and a negative electrode containing a material capable of occluding and releasing lithium ions,
Charging the lithium ion battery;
For a charged lithium ion battery, a step of partially discharging 0.1% or more of the total battery capacity;
Measuring the open electromotive force of a partially discharged lithium ion battery;
Calculating a remaining capacity from the open electromotive force;
including.
本実施形態に係る蓄電システムは、層状岩塩型構造を有する、下記式（１）
ＬｉｘＭ１ ｙＭ２ ｚＯ２−ｄ （１）
（前記式（１）において、１．１６≦ｘ≦１．３２、０．３３≦ｙ≦０．６３、０．０６≦ｚ≦０．３１及び０≦ｄ≦０．２０である。Ｍ１はＭｎ、Ｔｉ及びＺｒからなる群から選択される少なくとも一種、Ｍ２はＦｅ、Ｃｏ、Ｎｉ及びＭｎからなる群から選択される少なくとも一種である。）
で示されるリチウム酸化物を含む正極と、リチウムイオンを吸蔵放出可能な材料を含む負極とを備えるリチウムイオン電池と、
前記リチウムイオン電池を充電する手段と、
前記リチウムイオン電池を充電する手段により充電されたリチウムイオン電池について、電池全容量の０．１％以上を一部放電する手段と、
前記リチウムイオン電池を一部放電する手段により一部放電されたリチウムイオン電池の開放起電力を測定する手段と、
前記開放起電力を測定する手段により測定された開放起電力から残存容量を算出する手段と、
を備える。
The power storage system according to the present embodiment has a layered rock salt structure and has the following formula (1)
Li x M 1 y M 2 z O 2-d (1)
(In the formula (1), 1.16 ≦ x ≦ 1.32, 0.33 ≦ y ≦ 0.63, 0.06 ≦ z ≦ 0.31 and 0 ≦ d ≦ 0.20. M 1 the Mn, at least one selected from the group consisting of Ti and Zr, M 2 is at least one selected from the group consisting of Fe, Co, Ni and Mn.)
A lithium ion battery comprising: a positive electrode comprising a lithium oxide represented by: a negative electrode comprising a material capable of occluding and releasing lithium ions;
Means for charging the lithium ion battery;
For the lithium ion battery charged by the means for charging the lithium ion battery, means for partially discharging 0.1% or more of the total battery capacity;
Means for measuring an open electromotive force of a lithium ion battery partially discharged by means for partially discharging the lithium ion battery;
Means for calculating a remaining capacity from the open electromotive force measured by the means for measuring the open electromotive force;
Is provided.
本実施形態によれば、開放起電力から簡単かつ正確に残存容量を測定することができる。 According to the present embodiment, the remaining capacity can be measured easily and accurately from the open electromotive force.
［リチウムイオン電池の残存容量の測定方法］
本実施形態に係るリチウムイオン電池の残存容量の測定方法は、層状岩塩型構造を有する、下記式（１）
ＬｉxＭ1 yＭ2 zＯ2-d （１）
（前記式（１）において、１．１６≦ｘ≦１．３２、０．３３≦ｙ≦０．６３、０．０６≦ｚ≦０．５０及び０≦ｄ≦０．２０である。Ｍ1はＭｎ、Ｔｉ及びＺｒからなる群から選択される少なくとも一種、Ｍ2はＦｅ、Ｃｏ、Ｎｉ及びＭｎからなる群から選択される少なくとも一種である。）
で示されるリチウム酸化物を含む正極と、リチウムイオンを吸蔵放出可能な材料を含む負極とを備えるリチウムイオン電池の残存容量の測定方法であって、リチウムイオン電池を充電する工程と、充電されたリチウムイオン電池について、電池全容量の０．１％以上を一部放電する工程と、一部放電されたリチウムイオン電池の開放起電力を測定する工程と、前記開放起電力から残存容量を算出する工程と、を含む。
[Measurement method of remaining capacity of lithium-ion battery]
The method for measuring the remaining capacity of a lithium ion battery according to the present embodiment has a layered rock salt structure and has the following formula (1).
Li x M 1 y M 2 z O 2-d (1)
(In the formula (1), 1.16 ≦ x ≦ 1.32, 0.33 ≦ y ≦ 0.63, 0.06 ≦ z ≦ 0.50 and 0 ≦ d ≦ 0.20. M 1 Is at least one selected from the group consisting of Mn, Ti and Zr, and M 2 is at least one selected from the group consisting of Fe, Co, Ni and Mn.)
A method for measuring a remaining capacity of a lithium ion battery comprising a positive electrode containing a lithium oxide and a negative electrode containing a material capable of occluding and releasing lithium ions, the step of charging the lithium ion battery, For a lithium ion battery, a step of partially discharging 0.1% or more of the total battery capacity, a step of measuring an open electromotive force of the partially discharged lithium ion battery, and calculating a remaining capacity from the open electromotive force And a process.
前記式（１）で示されるリチウム酸化物を主成分とする正極と、リチウムイオンを吸蔵放出可能な材料を主成分とする負極とを備えるリチウムイオン電池は、充放電曲線に大きなヒステリシスが生じる。このため、開放起電力から残存容量を測定することが困難である。本実施形態に係る方法によれば、充放電曲線に大きなヒステリシスが生じる前記リチウムイオン電池においても、開放起電力と残存容量とを一義的に対応させることができるため、開放起電力から比較的簡単かつ正確に残存容量を測定することができる。 A lithium ion battery including a positive electrode mainly composed of a lithium oxide represented by the formula (1) and a negative electrode mainly composed of a material capable of occluding and releasing lithium ions has a large hysteresis in a charge / discharge curve. For this reason, it is difficult to measure the remaining capacity from the open electromotive force. According to the method according to the present embodiment, even in the lithium ion battery in which a large hysteresis occurs in the charge / discharge curve, the open electromotive force and the remaining capacity can be uniquely associated with each other. In addition, the remaining capacity can be accurately measured.
（リチウムイオン電池）
本実施形態に係るリチウムイオン電池の一例の断面図を図１に示す。図１に示されるリチウムイオン電池は積層構造のリチウムイオン電池である。該リチウムイオン電池は、層状岩塩型構造を有する前記式（１）で示されるリチウム酸化物を含む正極１と、正極集電体１Ａと、正極タブ１Ｂと、リチウムイオンを吸蔵放出可能な材料を含む負極２と、負極集電体２Ａと、負極タブ２Ｂと、セパレータ３と、外装体４とを備える。正極１は正極集電体１Ａ上に形成されている。負極２は負極集電体２Ａ上に形成されている。正極１と負極２との間にはセパレータ３が挟まれている。正極集電体１Ａには正極タブ１Ｂが接続されている。負極集電体２Ａには負極タブ２Ｂが接続されている。正極１、正極集電体１Ａ、正極タブ１Ｂ、負極２、負極集電体２Ａ及び負極タブ２Ｂを備える発電要素は、正極タブ１Ｂ及び負極タブ２Ｂの一部が外部に露出した状態で外装体４に覆われている。外装体４内は不図示の電解液で満たされている。
(Lithium ion battery)
FIG. 1 shows a cross-sectional view of an example of a lithium ion battery according to this embodiment. The lithium ion battery shown in FIG. 1 is a lithium ion battery having a laminated structure. The lithium ion battery includes a positive electrode 1 including a lithium oxide represented by the formula (1) having a layered rock salt structure, a positive electrode current collector 1A, a positive electrode tab 1B, and a material capable of occluding and releasing lithium ions. The negative electrode 2 containing, 2 A of negative electrode collectors, the negative electrode tab 2B, the separator 3, and the exterior body 4 are provided. The positive electrode 1 is formed on the positive electrode current collector 1A. The negative electrode 2 is formed on the negative electrode current collector 2A. A separator 3 is sandwiched between the positive electrode 1 and the negative electrode 2. A positive electrode tab 1B is connected to the positive electrode current collector 1A. A negative electrode tab 2B is connected to the negative electrode current collector 2A. The power generation element including the positive electrode 1, the positive electrode current collector 1 </ b> A, the positive electrode tab 1 </ b> B, the negative electrode 2, the negative electrode current collector 2 </ b> A, and the negative electrode tab 2 </ b> B is exposed in a state where a part of the positive electrode tab 1 </ b> B 4 is covered. The exterior body 4 is filled with an electrolyte solution (not shown).
本実施形態に係る正極は、正極活物質として、層状岩塩型構造を有する前記式（１）で示されるリチウム酸化物を含む。前記式（１）において、高い容量が得られる観点からＭ1はＭｎを少なくとも含むことが好ましい。また、安定性をより向上させる観点からＭ1はＭｎ及びＴｉを少なくとも含むことがより好ましい。前記式（１）において、低コストである観点からＭ2はＦｅを少なくとも含むことが好ましい。また、安定性をより向上させる観点からＭ2はＦｅ及びＮｉを少なくとも含むことがより好ましい。 The positive electrode according to the present embodiment includes a lithium oxide represented by the above formula (1) having a layered rock salt structure as a positive electrode active material. In the formula (1), M 1 preferably contains at least Mn from the viewpoint of obtaining a high capacity. Further, from the viewpoint of further improving the stability, M 1 more preferably contains at least Mn and Ti. In the formula (1), M 2 preferably contains at least Fe from the viewpoint of low cost. Further, from the viewpoint of further improving the stability, M 2 preferably contains at least Fe and Ni.
前記式（１）において、１．１７≦ｘ≦１．３０が好ましく、１．１８≦ｘ≦１．２８がより好ましく、１．１９≦ｘ≦１．２６がさらに好ましい。０．３５≦ｙ≦０．６０が好ましく、０．３７≦ｙ≦０．５８がより好ましく、０．３９≦ｙ≦０．５６がさらに好ましい。０．１０≦ｚ≦０．４８が好ましく、０．１４≦ｚ≦０．４６がより好ましく、０．１８≦ｚ≦０．４４がさらに好ましい。０≦ｄ≦０．１５が好ましく、０≦ｄ≦０．１２がより好ましく、０≦ｄ≦０．１０がさらに好ましい。 In the formula (1), 1.17 ≦ x ≦ 1.30 is preferable, 1.18 ≦ x ≦ 1.28 is more preferable, and 1.19 ≦ x ≦ 1.26 is further preferable. 0.35 ≦ y ≦ 0.60 is preferable, 0.37 ≦ y ≦ 0.58 is more preferable, and 0.39 ≦ y ≦ 0.56 is still more preferable. 0.10 ≦ z ≦ 0.48 is preferable, 0.14 ≦ z ≦ 0.46 is more preferable, and 0.18 ≦ z ≦ 0.44 is still more preferable. 0 ≦ d ≦ 0.15 is preferable, 0 ≦ d ≦ 0.12 is more preferable, and 0 ≦ d ≦ 0.10 is still more preferable.
前記式（１）で示されるリチウム酸化物の具体例としては、Ｌｉ1.19Ｍｎ0.52Ｆｅ0.22Ｏ2、Ｌｉ1.20Ｍｎ0.40Ｆｅ0.40Ｏ2.00、Ｌｉ1.23Ｍｎ0.46Ｆｅ0.31Ｏ2.00、Ｌｉ1.29Ｍｎ0.57Ｆｅ0.14Ｏ2.00、Ｌｉ1.20Ｍｎ0.40Ｎｉ0.40Ｏ2.00、Ｌｉ1.23Ｍｎ0.46Ｎｉ0.31Ｏ2.00、Ｌｉ1.26Ｍｎ0.52Ｎｉ0.22Ｏ2.00、Ｌｉ1.29Ｍｎ0.57Ｎｉ0.14Ｏ2.00、Ｌｉ1.20Ｍｎ0.60Ｎｉ0.20Ｏ2.00、Ｌｉ1.23Ｍｎ0.61Ｎｉ0.15Ｏ2.00、Ｌｉ1.26Ｍｎ0.63Ｎｉ0.11Ｏ2.00、Ｌｉ1.20Ｍｎ0.40Ｆｅ0.20Ｎｉ0.20Ｏ2.00、Ｌｉ1.23Ｍｎ0.46Ｆｅ0.15Ｎｉ0.15Ｏ2.00、Ｌｉ1.26Ｍｎ0.52Ｆｅ0.11Ｎｉ0.11Ｏ2.00、Ｌｉ1.29Ｍｎ0.57Ｆｅ0.07Ｎｉ0.14Ｏ2.00、Ｌｉ1.26Ｍｎ0.37Ｔｉ0.15Ｎｉ0.22Ｏ2.00、Ｌｉ1.26Ｍｎ0.37Ｔｉ0.15Ｆｅ0.22Ｏ2.00、Ｌｉ1.23Ｍｎ0.33Ｔｉ0.13Ｆｅ0.15Ｎｉ0.15Ｏ2.00、Ｌｉ1.20Ｍｎ0.56Ｎｉ0.17Ｃｏ0.07Ｏ2.00、Ｌｉ1.20Ｍｎ0.54Ｎｉ0.13Ｃｏ0.13Ｏ2.00等が挙げられる。これらの正極活物質は、一種のみを用いてもよく、二種以上を併用してもよい。 Specific examples of the lithium oxide represented by the formula (1) include Li 1.19 Mn 0.52 Fe 0.22 O 2 , Li 1.20 Mn 0.40 Fe 0.40 O 2.00 , Li 1.23 Mn 0.46 Fe 0.31 O 2.00 , Li 1.29 Mn 0.57 Fe 0.14 O 2.00 , Li 1.20 Mn 0.40 Ni 0.40 O 2.00 , Li 1.23 Mn 0.46 Ni 0.31 O 2.00 , Li 1.26 Mn 0.52 Ni 0.22 O 2.00 , Li 1.29 Mn 0.57 Ni 0.14 O 2.00 , Li 1.20 Mn 0.60 Ni 0.20 O 2.00 , Li 1.23 Mn 0.61 Ni 0.15 O 2.00 , Li 1.26 Mn 0.63 Ni 0.11 O 2.00 , Li 1.20 Mn 0.40 Fe 0.20 Ni 0.20 O 2.00 , Li 1.23 Mn 0.46 Fe 0.15 Ni 0.15 O 2.00 , Li 1.26 Mn 0.52 Fe 0.11 Ni 0.11 O 2.00 , Li 1.29 Mn 0.57 Fe 0.07 Ni 0.14 O 2.00 , Li 1.26 Mn 0.37 Ti 0.15 Ni 0.22 O 2.00 , Li 1.26 Mn 0.37 Ti 0.15 Fe 0.22 O 2.00 , Li 1.23 Mn 0.33 Ti 0.1 3 Fe 0.15 Ni 0.15 O 2.00 , Li 1.20 Mn 0.56 Ni 0.17 Co 0.07 O 2.00 , Li 1.20 Mn 0.54 Ni 0.13 Co 0.13 O 2.00, and the like. These positive electrode active materials may be used alone or in combination of two or more.
また、高容量が得られる観点から、前記式（１）で示されるリチウム酸化物としては、Ｘ線粉末回折法で測定した場合、２０〜２４°の領域にブロードなピークを有するリチウム酸化物が好ましい。 Further, from the viewpoint of obtaining a high capacity, the lithium oxide represented by the formula (1) is a lithium oxide having a broad peak in the region of 20 to 24 ° when measured by an X-ray powder diffraction method. preferable.
前記式（１）で示されるリチウム酸化物が層状岩塩型構造を有することは、粉末Ｘ線回折法により確認することができる。 It can be confirmed by a powder X-ray diffraction method that the lithium oxide represented by the formula (1) has a layered rock salt structure.
本実施形態に係る正極集電体の材料としては、アルミニウム、アルミニウム合金、ステンレス等を用いることができる。正極集電体の形状としては、箔、平板、メッシュ状が挙げられる。また、電池内部で発生するガスの通気性を向上させる観点から、表裏面を貫通する孔を備える正極集電体を用いることもできる。該表裏面を貫通する孔を備える正極集電体としては、例えば、エキスパンドメタル、パンチングメタル、金属網、発泡体、エッチングにより貫通孔が付与された多孔質箔等が挙げられる。 As a material of the positive electrode current collector according to this embodiment, aluminum, an aluminum alloy, stainless steel, or the like can be used. Examples of the shape of the positive electrode current collector include a foil, a flat plate, and a mesh. In addition, from the viewpoint of improving the gas permeability generated inside the battery, a positive electrode current collector having holes penetrating the front and back surfaces can also be used. Examples of the positive electrode current collector having holes penetrating the front and back surfaces include expanded metal, punching metal, metal net, foam, and porous foil provided with through holes by etching.
本実施形態に係る正極の作製方法は特に限定されない。例えば、前記正極活物質、結着剤及び導電性付与剤を含む混合物と、溶媒とを含むインクを調製し、該インクを正極集電体に塗布し、溶媒を乾燥することで作製することができる。 The method for producing the positive electrode according to this embodiment is not particularly limited. For example, it can be prepared by preparing an ink containing a mixture containing the positive electrode active material, a binder and a conductivity-imparting agent and a solvent, applying the ink to a positive electrode current collector, and drying the solvent. it can.
結着剤としては、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン（ＰＴＦＥ）、ビニリデンフロライド−ヘキサフルオロプロピレン共重合体、スチレン−ブタジエン共重合ゴム、ポリプロピレン、ポリエチレン、ポリアクリロニトリル等を用いることができる。導電性付与剤としては、例えば、ケッチェンブラック、気相成長炭素繊維、カーボンブラック、ファーネスブラック、カーボンナノチューブ、黒鉛、難黒鉛化炭素、金属粉末等を用いることができる。溶媒としては、例えば水、Ｎメチルピロリドン等を用いることができる。これらは一種のみを用いてもよく、二種以上を併用してもよい。 As the binder, for example, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), vinylidene fluoride-hexafluoropropylene copolymer, styrene-butadiene copolymer rubber, polypropylene, polyethylene, polyacrylonitrile and the like can be used. . Examples of the conductivity imparting agent include ketjen black, vapor grown carbon fiber, carbon black, furnace black, carbon nanotube, graphite, non-graphitizable carbon, metal powder, and the like. As the solvent, for example, water, N methylpyrrolidone, or the like can be used. These may use only 1 type and may use 2 or more types together.
正極に含まれる正極活物質の量は、特に限定されないが、十分な容量が得られる観点から正極全体の質量に対して５０質量％以上であることが好ましい。また、より大きな容量が得られる観点から、正極全体の質量に対して７０質量％以上であることがより好ましく、８５質量％以上であることがさらに好ましい。また、正極に含まれる正極活物質の量の上限は特に限定されないが、例えば９９質量％以下とすることができる。 The amount of the positive electrode active material contained in the positive electrode is not particularly limited, but is preferably 50% by mass or more based on the total mass of the positive electrode from the viewpoint of obtaining a sufficient capacity. Further, from the viewpoint of obtaining a larger capacity, it is more preferably 70% by mass or more, and further preferably 85% by mass or more with respect to the mass of the entire positive electrode. Moreover, the upper limit of the amount of the positive electrode active material contained in the positive electrode is not particularly limited, but may be 99% by mass or less, for example.
正極の厚みは特に限定されないが、十分な容量が得られる観点から２０μｍ以上であることが好ましい。また、より大きな容量が得られる観点から、５０μｍ以上であることがより好ましく、７０μｍ以上であることがさらに好ましい。また、正極の厚みの上限は特に限定されないが、例えば５００μｍ以下とすることができる。 The thickness of the positive electrode is not particularly limited, but is preferably 20 μm or more from the viewpoint of obtaining a sufficient capacity. Further, from the viewpoint of obtaining a larger capacity, it is more preferably 50 μm or more, and further preferably 70 μm or more. Moreover, the upper limit of the thickness of the positive electrode is not particularly limited, but can be, for example, 500 μm or less.
本実施形態に係る負極は、負極活物質として、リチウムイオンを吸蔵放出可能な材料を含む。リチウムイオンを吸蔵放出可能な材料としては、例えば人造黒鉛、天然黒鉛、ハードカーボン、活性炭等の炭素材料、ポリアセン、ポリアセチレン、ポリフェニレン、ポリアニリン、ポリピロール等の導電性高分子、シリコン、スズ、アルミニウム等のリチウム金属と合金を形成する合金材料、チタン酸リチウム等のリチウム酸化物、およびリチウム金属等を用いることができる。これらは一種のみを用いてもよく、二種以上を併用してもよい。また、これらの炭素材料、又はリチウム金属と合金を形成する合金材料には、予めリチウムイオンがドープされていてもよい。 The negative electrode according to the present embodiment includes a material capable of occluding and releasing lithium ions as the negative electrode active material. Examples of materials that can occlude and release lithium ions include carbon materials such as artificial graphite, natural graphite, hard carbon, and activated carbon, conductive polymers such as polyacene, polyacetylene, polyphenylene, polyaniline, and polypyrrole, silicon, tin, and aluminum. An alloy material which forms an alloy with lithium metal, lithium oxide such as lithium titanate, lithium metal, or the like can be used. These may use only 1 type and may use 2 or more types together. Further, lithium ions may be doped in advance in these carbon materials or alloy materials that form an alloy with lithium metal.
本実施形態に係る負極集電体の材料としては、銅、ニッケル、ステンレス等を用いることができる。負極集電体の形状としては、箔、平板、メッシュ状が挙げられる。また、電池内部で発生するガスの通気性を向上させる観点から、表裏面を貫通する孔を備える負極集電体を用いることもできる。該表裏面を貫通する孔を備える負極集電体としては、例えば、エキスパンドメタル、パンチングメタル、金属網、発泡体、エッチングにより貫通孔が付与された多孔質箔等が挙げられる。 As a material of the negative electrode current collector according to the present embodiment, copper, nickel, stainless steel, or the like can be used. Examples of the shape of the negative electrode current collector include a foil, a flat plate, and a mesh. Further, from the viewpoint of improving the gas permeability generated in the battery, a negative electrode current collector having holes penetrating the front and back surfaces can also be used. Examples of the negative electrode current collector having holes penetrating the front and back surfaces include expanded metal, punching metal, metal net, foam, porous foil provided with through holes by etching, and the like.
本実施形態に係る負極の作製方法は特に限定されない。例えば、前記負極活物質、結着剤及び導電性付与剤を含む混合物と、溶媒とを含むインクを調製し、該インクを負極集電体に塗布し、溶媒を乾燥することで作製することができる。 The method for producing the negative electrode according to this embodiment is not particularly limited. For example, it is possible to prepare an ink containing a mixture containing the negative electrode active material, a binder and a conductivity imparting agent and a solvent, applying the ink to a negative electrode current collector, and drying the solvent. it can.
結着剤としては、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン（ＰＴＦＥ）、ビニリデンフロライド−ヘキサフルオロプロピレン共重合体、スチレン−ブタジエン共重合ゴム、ポリプロピレン、ポリエチレン、ポリアクリロニトリル、ポリイミド、ポリアミドイミド等を用いることができる。導電性付与剤としては、例えば、ケッチェンブラック、カーボンブラック、アセチレンブラック、ファーネスブラック、カーボンナノチューブ、金属粉末等を用いることができる。溶媒としては、例えば水、Ｎメチルピロリドン等を用いることができる。これらは一種のみを用いてもよく、二種以上を併用してもよい。 Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene (PTFE), vinylidene fluoride-hexafluoropropylene copolymer, styrene-butadiene copolymer rubber, polypropylene, polyethylene, polyacrylonitrile, polyimide, and polyamideimide. Can be used. Examples of the conductivity-imparting agent that can be used include ketjen black, carbon black, acetylene black, furnace black, carbon nanotube, and metal powder. As the solvent, for example, water, N methylpyrrolidone, or the like can be used. These may use only 1 type and may use 2 or more types together.
負極に含まれる負極活物質の量は、特に限定されないが、十分な容量が得られる観点から負極全体の質量に対して７０質量％以上であることが好ましい。また、より大きな容量が得られる観点から、負極全体の質量に対して８０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。また、負極に含まれる負極活物質の量の上限は特に限定されないが、例えば９９質量％以下とすることができる。 The amount of the negative electrode active material contained in the negative electrode is not particularly limited, but is preferably 70% by mass or more based on the total mass of the negative electrode from the viewpoint of obtaining sufficient capacity. Further, from the viewpoint of obtaining a larger capacity, it is more preferably 80% by mass or more, and further preferably 90% by mass or more with respect to the mass of the whole negative electrode. Moreover, the upper limit of the amount of the negative electrode active material contained in the negative electrode is not particularly limited, but may be, for example, 99% by mass or less.
負極の厚みは特に限定されないが、十分な容量が得られる観点から３０μｍ以上であることが好ましい。また、より大きな容量が得られる観点から、５０μｍ以上であることがより好ましく、７０μｍ以上であることがさらに好ましい。また、負極の厚みの上限は特に限定されないが、例えば５００μｍ以下とすることができる。 The thickness of the negative electrode is not particularly limited, but is preferably 30 μm or more from the viewpoint of obtaining a sufficient capacity. Further, from the viewpoint of obtaining a larger capacity, it is more preferably 50 μm or more, and further preferably 70 μm or more. Moreover, the upper limit of the thickness of the negative electrode is not particularly limited, but may be, for example, 500 μm or less.
本実施形態に係るセパレータとしては、正極負極間に介在させることで、電子を伝導させずにイオンのみを伝導させる役割を果たすことのできるセパレータであれば特に限定されない。セパレータとしては、例えば多孔質フィルムセパレータを用いることができる。多孔質フィルムセパレータとしては、例えばポリプロピレン、ポリエチレン等のポリオレフィンの多孔質膜、アラミド樹脂フィルム、フッ素樹脂等の多孔性フィルム等が挙げられる。 The separator according to the present embodiment is not particularly limited as long as it is a separator that can play a role of conducting only ions without conducting electrons by being interposed between positive and negative electrodes. As the separator, for example, a porous film separator can be used. Examples of the porous film separator include a porous film of polyolefin such as polypropylene and polyethylene, a porous film of aramid resin film, fluororesin, and the like.
本実施形態に係る電解液としては、特に限定されないが、リチウム塩が溶媒中に溶解された溶液を用いることができる。リチウム塩としては、例えば、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、ＬｉＣ（Ｃ2Ｆ5ＳＯ2）3等を用いることができる。これらは一種のみを用いてもよく、二種以上を併用してもよい。溶媒としては、エチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、プロピレンカーボネート、ジエチルカーボネート、メチルエチルカーボネート、γ−ブチロラクトン、テトラヒドロフラン、ジオキソラン、スルホラン、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン等の有機溶媒、フッ素化溶媒等を用いることができる。これらは一種のみを用いてもよく、二種以上を併用してもよい。 Although it does not specifically limit as electrolyte solution which concerns on this embodiment, The solution in which lithium salt was melt | dissolved in the solvent can be used. Examples of the lithium salt include LiPF 6 , LiBF 4 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 or the like can be used. These may use only 1 type and may use 2 or more types together. Examples of the solvent include ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and the like. These organic solvents, fluorinated solvents, and the like can be used. These may use only 1 type and may use 2 or more types together.
電解液中に含まれるリチウム塩の濃度としては、特に限定されないが、電解液が室温で１０-5〜１０-1Ｓ／ｃｍのイオン伝導性を示し、正極と負極との間の荷電担体輸送を十分に行うことができる観点から、０．５〜１．５ｍｏｌ／ｌであることが好ましい。 The concentration of the lithium salt contained in the electrolytic solution is not particularly limited, but the electrolytic solution exhibits an ionic conductivity of 10 −5 to 10 −1 S / cm at room temperature, and charge carrier transport between the positive electrode and the negative electrode Is preferably 0.5 to 1.5 mol / l from the viewpoint of sufficiently performing the above.
なお、電解液の代わりにゲル電解質を用いてもよい。ゲル電解質としては、例えば、前記電解液を、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体等のフッ化ビニリデン系重合体、アクリロニトリル−メチルメタクリレート共重合体、アクリロニトリル−メチルアクリレート共重合体等のアクリルニトリル系重合体、ポリエチレンオキサイド等の高分子材料に含ませてゲル状にした電解質を用いることができる。前記高分子材料は一種のみを用いてもよく、二種以上を併用してもよい。 A gel electrolyte may be used instead of the electrolytic solution. As the gel electrolyte, for example, the electrolyte solution is made of a polyvinylidene fluoride, a vinylidene fluoride polymer such as a vinylidene fluoride-hexafluoropropylene copolymer, an acrylonitrile-methyl methacrylate copolymer, an acrylonitrile-methyl acrylate copolymer. It is possible to use an electrolyte that is gelled by being included in a polymer material such as an acrylonitrile polymer such as polyethylene oxide. The polymer material may be used alone or in combination of two or more.
本実施形態に係る外装体としては、特に限定されないが、例えば金属ケース、樹脂ケース等が挙げられる。外装体の材料としては、例えば鉄、アルミニウム等の金属材料、プラスチック材料、ガラス材料、それらの材料を積層した複合材料等が挙げられる。しかしながら、後述する酸化処理後のガス抜き作業を簡便に行うことができる観点から、アルミニウムとナイロン、ポリプロピレン等の高分子フィルムとを積層させたアルミニウムラミネートフィルムが好ましい。 Although it does not specifically limit as an exterior body which concerns on this embodiment, For example, a metal case, a resin case, etc. are mentioned. Examples of the material of the exterior body include metal materials such as iron and aluminum, plastic materials, glass materials, and composite materials obtained by stacking these materials. However, an aluminum laminate film obtained by laminating aluminum and a polymer film such as nylon or polypropylene is preferable from the viewpoint that the degassing operation after the oxidation treatment described later can be easily performed.
本実施形態に係るリチウムイオン電池の作製方法は特に限定されない。例えば、正極、正極集電体、負極及び負極集電体を、セパレータを介して積層する。正極集電体に正極タブを、負極集電体に負極タブを溶接することで発電要素を作製する。該発電要素を外装体で包み、３辺を熱融着により封止する。その後、減圧下、該発電要素に電解質を含浸させ、残りの１辺を熱融着して封止することで、リチウムイオン電池を作製することができる。 The method for producing the lithium ion battery according to this embodiment is not particularly limited. For example, a positive electrode, a positive electrode current collector, a negative electrode, and a negative electrode current collector are stacked via a separator. A power generation element is fabricated by welding a positive electrode tab to the positive electrode current collector and a negative electrode tab to the negative electrode current collector. The power generation element is wrapped with an exterior body, and the three sides are sealed by thermal fusion. Then, under reduced pressure, the power generation element is impregnated with an electrolyte, and the remaining one side is heat-sealed and sealed, whereby a lithium ion battery can be manufactured.
発電要素は積層型以外にも、捲回型、折り畳み型等とすることもできるが、放熱性が優れる観点から積層型が好ましい。リチウムイオン電池の外観は特に限定されないが、例えば角型、円筒型、コイン型、シート型等が挙げられる。 The power generation element can be a wound type, a folded type, or the like in addition to the laminated type, but the laminated type is preferable from the viewpoint of excellent heat dissipation. The appearance of the lithium ion battery is not particularly limited, and examples thereof include a rectangular shape, a cylindrical shape, a coin shape, and a sheet shape.
なお、本実施形態においてリチウムイオン電池とは、リチウムイオン二次電池を含む。 In this embodiment, the lithium ion battery includes a lithium ion secondary battery.
（酸化処理）
本実施形態に係るリチウムイオン電池は、電気化学的に酸化処理されていることが好ましい。電気化学的に酸化処理されているとは、リチウムイオン電池の正極、負極間に電圧を印加することで、正極を酸化させる処理が施されていることを示す。該酸化処理は、低コストで酸化処理できる観点から、例えば、以下のプレサイクル法により行うことができる。まず、リチウムイオン電池に対し、正極活物質あたり２０ｍＡ／ｇの電流で４．２Ｖまで充電し、正極活物質あたり２０ｍＡ／ｇの電流で２．０Ｖまで放電する。これを１サイクルとする。次のサイクル以降は上限電圧を０．１Ｖずつ上昇させる。すなわち、次のサイクルでは４．３Ｖまで充電し２．０Ｖまで放電し、その次のサイクルでは４．４Ｖまで充電し２．０Ｖまで放電する。最終的に上限電圧が４．８Ｖになるまで７サイクルを繰り返す。酸化処理後のリチウムイオン電池は、一旦封口部を破り減圧することで電池内部のガスを抜き、再封口することができる。なお、前記プレサイクル法において、上限電圧の範囲や電流値、サイクル数、温度等は特に限定されない。
(Oxidation treatment)
The lithium ion battery according to this embodiment is preferably electrochemically oxidized. Being electrochemically oxidized means that a treatment for oxidizing the positive electrode is performed by applying a voltage between the positive electrode and the negative electrode of the lithium ion battery. The oxidation treatment can be performed, for example, by the following precycle method from the viewpoint of being able to perform the oxidation treatment at a low cost. First, a lithium ion battery is charged to 4.2 V at a current of 20 mA / g per positive electrode active material and discharged to 2.0 V at a current of 20 mA / g per positive electrode active material. This is one cycle. After the next cycle, the upper limit voltage is increased by 0.1V. That is, in the next cycle, the battery is charged to 4.3V and discharged to 2.0V, and in the next cycle, the battery is charged to 4.4V and discharged to 2.0V. 7 cycles are repeated until the upper limit voltage finally reaches 4.8V. After the oxidation treatment, the lithium ion battery can be re-sealed by breaking the sealing portion and depressurizing to release the gas inside the battery. In the precycle method, the range of the upper limit voltage, the current value, the number of cycles, the temperature, and the like are not particularly limited.
（充電工程）
本実施形態に係る方法は、リチウムイオン電池を充電する工程（以下、充電工程と示す）を含む。
(Charging process)
The method according to the present embodiment includes a step of charging a lithium ion battery (hereinafter referred to as a charging step).
充電工程における充電条件は特に限定されないが、正極活物質あたり１０〜７０ｍＡ／ｇの電流で充電することが好ましく、２０〜６０ｍＡ／ｇの電流で充電することがより好ましい。電池全容量に対する充電容量の割合は、特に限定されないが、５〜１００％が好ましく、１０〜９０％がより好ましい。なお、リチウムイオン電池の電池全容量は、１０ｍＡ／ｇのレートで充放電した際の放電容量より求めた値とする。 Charging conditions in the charging step are not particularly limited, but charging with a current of 10 to 70 mA / g per positive electrode active material is preferable, and charging with a current of 20 to 60 mA / g is more preferable. The ratio of the charge capacity to the total battery capacity is not particularly limited, but is preferably 5 to 100%, more preferably 10 to 90%. In addition, let the battery total capacity | capacitance of a lithium ion battery be the value calculated | required from the discharge capacity at the time of charging / discharging at the rate of 10 mA / g.
（一部放電工程）
本実施形態に係る方法は、前記充電されたリチウムイオン電池について、電池全容量の０．１％以上を一部放電する工程（以下、一部放電工程と示す）を含む。
(Partial discharge process)
The method according to the present embodiment includes a step of partially discharging 0.1% or more of the total capacity of the charged lithium ion battery (hereinafter referred to as a partial discharge step).
一部放電工程において、電池全容量の０．１％以上を一部放電する。これにより、充放電曲線に大きなヒステリシスが生じる本実施形態に係るリチウムイオン電池においても、開放起電力と残存容量とを一義的に対応させることができる。一部放電工程では、電池全容量の１％以上を一部放電することが好ましく、電池全容量の２％以上を一部放電することがより好ましく、電池全容量の４％以上を一部放電することがさらに好ましい。一方、一部放電する際に放電容量が多ければ多いほど開放起電力からより正確に残存容量を測定することが可能になるものの、無駄に捨てるエネルギー量が多くなるため、電池全容量の２０％以下を一部放電することが好ましく、電池全容量の１５％以下を一部放電することがより好ましく、電池全容量の１０％以下を一部放電することがさらに好ましい。 In the partial discharge process, 0.1% or more of the total battery capacity is partially discharged. Thereby, also in the lithium ion battery which concerns on this embodiment which a big hysteresis arises in a charging / discharging curve, an open electromotive force and a remaining capacity can be made to respond | correspond uniquely. In the partial discharge process, it is preferable to partially discharge 1% or more of the total battery capacity, more preferably 2% or more of the total battery capacity, and partial discharge of 4% or more of the total battery capacity. More preferably. On the other hand, the more the discharge capacity is, the more the remaining capacity can be measured from the open electromotive force when partially discharging, but the amount of energy that is wasted is increased, so 20% of the total capacity of the battery. The following is preferably partially discharged, more preferably 15% or less of the total battery capacity is partially discharged, and further preferably 10% or less of the total battery capacity is partially discharged.
一部放電工程における放電条件は特に限定されないが、正極活物質あたり１０〜７０ｍＡ／ｇの電流で放電することが好ましく、２０〜６０ｍＡ／ｇの電流で放電することがより好ましい。一部放電後の実際の残存容量（以下、実残存容量と示す）は、特に限定されず、電池全容量に対し０％を超えて９９．９％以下とすることができる。しかしながら、開放起電力と残存容量とをより一義的に対応させることができる観点から、一部放電後の実残存容量は電池全容量に対し、６％以上、９０％以下であることが好ましく、１２％以上、７５％以下であることがより好ましい。なお、実残存容量は、充電容量から一部放電容量を差し引くことにより算出することができる。また、実残存容量が０となる放電は、本実施形態における一部放電には含まれない。 The discharge conditions in the partial discharge step are not particularly limited, but discharging is preferably performed at a current of 10 to 70 mA / g per positive electrode active material, and more preferably discharged at a current of 20 to 60 mA / g. The actual remaining capacity after partial discharge (hereinafter referred to as the actual remaining capacity) is not particularly limited, and may be more than 0% and 99.9% or less with respect to the total battery capacity. However, from the viewpoint that the open electromotive force and the remaining capacity can be more uniquely associated, the actual remaining capacity after partial discharge is preferably 6% or more and 90% or less with respect to the total battery capacity, More preferably, it is 12% or more and 75% or less. The actual remaining capacity can be calculated by subtracting a part of the discharge capacity from the charge capacity. Moreover, the discharge in which the actual remaining capacity becomes 0 is not included in the partial discharge in the present embodiment.
（開放起電力測定工程）
本実施形態に係る方法は、一部放電されたリチウムイオン電池の開放起電力を測定する工程（以下、開放起電力測定工程と示す）を含む。
(Open electromotive force measurement process)
The method according to the present embodiment includes a step of measuring an open electromotive force of a partially discharged lithium ion battery (hereinafter referred to as an open electromotive force measurement step).
開放起電力測定工程におけるリチウムイオン電池の開放起電力は、電子回路により測定することができる。リチウムイオン電池を開回路状態で１時間以上放置して開放起電力を測定することが好ましい。 The open electromotive force of the lithium ion battery in the open electromotive force measurement step can be measured by an electronic circuit. It is preferable to measure the open electromotive force by leaving the lithium ion battery in an open circuit state for 1 hour or more.
（残存容量算出工程）
本実施形態に係る方法は、前記開放起電力から残存容量を算出する工程（以下、残存容量算出工程と示す）を含む。
(Remaining capacity calculation process)
The method according to the present embodiment includes a step of calculating a remaining capacity from the open electromotive force (hereinafter referred to as a remaining capacity calculating step).
充放電ヒステリシスがないリチウムイオン電池では、開放起電力と残存容量とが一義的に対応するため、充電途中の場合でも放電途中の場合でも、開放起電力を測定することによって比較的簡単かつ正確に残存容量を測定することができる。しかしながら、充放電ヒステリシスのあるリチウムイオン電池では、開放起電力と残存容量とが一義的に対応しないため、開放起電力を測定しても正確に残存容量を測定することができない。本実施形態に係る方法を用いれば、充放電ヒステリシスがある本実施形態に係るリチウムイオン電池においても、実質的に開放起電力と残存容量とを対応させることができる。このため、充放電ヒステリシスがない電池と同様に、開放起電力を測定することによって比較的簡単かつ正確に残存容量を測定することができる。 In lithium ion batteries without charge / discharge hysteresis, the open electromotive force and the remaining capacity correspond unambiguously, so it is relatively easy and accurate to measure the open electromotive force during charging and during discharging. The remaining capacity can be measured. However, in a lithium ion battery having charge / discharge hysteresis, the open electromotive force and the remaining capacity do not uniquely correspond to each other, and therefore the remaining capacity cannot be measured accurately even if the open electromotive force is measured. By using the method according to the present embodiment, the open electromotive force and the remaining capacity can be substantially matched in the lithium ion battery according to the present embodiment having charge / discharge hysteresis. For this reason, the remaining capacity can be measured relatively easily and accurately by measuring the open electromotive force in the same manner as a battery without charge / discharge hysteresis.
測定した開放起電力から残存容量を算出する方法については特に限定されないが、例えば開放起電力と残存容量とを対応させて表示する電子回路等を使って算出することができる。 The method for calculating the remaining capacity from the measured open electromotive force is not particularly limited. For example, the remaining capacity can be calculated using an electronic circuit that displays the open electromotive force and the remaining capacity in correspondence with each other.
なお、同じ残存容量を有するリチウムイオン電池の開放起電力を比較した場合、その開放起電力の許容誤差としては、±０．２Ｖ以内であることが好ましい。より正確に残存容量を算出できる観点から、許容誤差は±０．１Ｖ以内であることがより好ましい。 When comparing the open electromotive force of lithium ion batteries having the same remaining capacity, the allowable error of the open electromotive force is preferably within ± 0.2V. From the viewpoint of more accurately calculating the remaining capacity, the tolerance is more preferably within ± 0.1V.
［蓄電システム］
本実施形態に係る蓄電システムは、層状岩塩型構造を有する、下記式（１）
ＬｉxＭ1 yＭ2 zＯ2-d （１）
（前記式（１）において、１．１６≦ｘ≦１．３２、０．３３≦ｙ≦０．６３、０．０６≦ｚ≦０．５０及び０≦ｄ≦０．２０である。Ｍ1はＭｎ、Ｔｉ及びＺｒからなる群から選択される少なくとも一種、Ｍ2はＦｅ、Ｃｏ、Ｎｉ及びＭｎからなる群から選択される少なくとも一種である。）
で示されるリチウム酸化物を含む正極と、リチウムイオンを吸蔵放出可能な材料を含む負極とを備えるリチウムイオン電池と、前記リチウムイオン電池を充電する手段（以下、充電手段と示す）と、前記充電手段により充電されたリチウムイオン電池について、電池全容量の０．１％以上を一部放電する手段（以下、一部放電手段と示す）と、前記一部放電手段により一部放電されたリチウムイオン電池の開放起電力を測定する手段（以下、開放起電力測定手段と示す）と、前記開放起電力測定手段により測定された開放起電力から残存容量を算出する手段（以下、残存容量算出手段と示す）と、を備える。
[Power storage system]
The power storage system according to the present embodiment has a layered rock salt structure and has the following formula (1)
Li x M 1 y M 2 z O 2-d (1)
(In the formula (1), 1.16 ≦ x ≦ 1.32, 0.33 ≦ y ≦ 0.63, 0.06 ≦ z ≦ 0.50 and 0 ≦ d ≦ 0.20. M 1 Is at least one selected from the group consisting of Mn, Ti and Zr, and M 2 is at least one selected from the group consisting of Fe, Co, Ni and Mn.)
A lithium ion battery comprising: a positive electrode containing a lithium oxide; and a negative electrode containing a material capable of occluding and releasing lithium ions; means for charging the lithium ion battery (hereinafter referred to as charging means); and the charging Regarding lithium ion batteries charged by the means, means for partially discharging 0.1% or more of the total capacity of the battery (hereinafter referred to as partial discharge means), and lithium ions partially discharged by the partial discharge means Means for measuring the open electromotive force of the battery (hereinafter referred to as open electromotive force measuring means), and means for calculating the remaining capacity from the open electromotive force measured by the open electromotive force measuring means (hereinafter referred to as remaining capacity calculating means). Show).
本実施形態に係る蓄電システムが備えるリチウムイオン電池としては、前記リチウムイオン電池を用いることができる。 The lithium ion battery can be used as the lithium ion battery included in the power storage system according to the present embodiment.
本実施形態に係る蓄電システムが備える充電手段としては、前記充電工程を行うことができる手段であれば特に限定されない。該手段としては、例えば、定電流充電法、定電流充電−定電圧充電法等による充電手段が挙げられる。 The charging unit provided in the power storage system according to the present embodiment is not particularly limited as long as it is a unit that can perform the charging step. Examples of the means include charging means by a constant current charging method, a constant current charging-constant voltage charging method, and the like.
本実施形態に係る蓄電システムが備える一部放電手段としては、前記一部放電工程を行うことができる手段であれば特に限定されない。該手段としては、例えば、定電流放電等による一部放電手段が挙げられる。 The partial discharge means provided in the power storage system according to the present embodiment is not particularly limited as long as it is a means capable of performing the partial discharge step. Examples of the means include partial discharge means by constant current discharge or the like.
本実施形態に係る蓄電システムが備える開放起電力測定手段としては、例えば、電子回路を用いることができる。 As an open electromotive force measuring means included in the power storage system according to the present embodiment, for example, an electronic circuit can be used.
本実施形態に係る蓄電システムが備える残存容量算出手段としては、前記残存容量算出工程を行うことができる手段であれば特に限定されない。該手段としては、例えば、電子回路を用いることができる。 The remaining capacity calculating means provided in the power storage system according to the present embodiment is not particularly limited as long as it is a means capable of performing the remaining capacity calculating step. For example, an electronic circuit can be used as the means.
本実施形態に係る蓄電システムの構成の一例を図２に示す。充電手段１１は、リチウムイオン電池１０に接続され、前記充電工程を行う。一部放電手段１２は、リチウムイオン電池１０に接続され、前記一部放電工程を行う。開放起電力測定手段１３は、リチウムイオン電池１０に接続され、一部放電後の開放起電力の測定を行う。残存容量算出手段１４は開放起電力測定手段１３に接続され、開放起電力測定手段１３により測定された開放起電力の値から残存容量を算出する。 An example of the configuration of the power storage system according to this embodiment is shown in FIG. The charging means 11 is connected to the lithium ion battery 10 and performs the charging step. The partial discharge means 12 is connected to the lithium ion battery 10 and performs the partial discharge step. The open electromotive force measuring means 13 is connected to the lithium ion battery 10 and measures the open electromotive force after partial discharge. The remaining capacity calculating means 14 is connected to the open electromotive force measuring means 13 and calculates the remaining capacity from the value of the open electromotive force measured by the open electromotive force measuring means 13.
なお、充電手段及び放電手段として、両者の機能を備える一つの装置を用いてもよい。また、開放起電力測定手段及び残存容量算出手段として、両者の機能を備える一つの装置を用いてもよい。また、充電手段、放電手段及び開放起電力測定手段として、３つの機能を備える一つの装置を用いてもよい。さらに、充電手段、放電手段、開放起電力測定手段及び残存容量算出手段として、４つの機能を備える一つの装置を用いてもよい。 In addition, you may use one apparatus provided with the function of both as a charging means and a discharge means. Moreover, you may use one apparatus provided with the function of both as an open electromotive force measurement means and a remaining capacity calculation means. Moreover, you may use one apparatus provided with three functions as a charging means, a discharge means, and an open electromotive force measurement means. Furthermore, a single device having four functions may be used as the charging means, discharging means, open electromotive force measurement means, and remaining capacity calculation means.
［リチウムイオン電池の充電方法］
本実施形態に係るリチウムイオン電池の充電方法は、層状岩塩型構造を有する、下記式（１）
ＬｉxＭ1 yＭ2 zＯ2-d （１）
（前記式（１）において、１．１６≦ｘ≦１．３２、０．３３≦ｙ≦０．６３、０．０６≦ｚ≦０．５０及び０≦ｄ≦０．２０である。Ｍ1はＭｎ、Ｔｉ及びＺｒからなる群から選択される少なくとも一種、Ｍ2はＦｅ、Ｃｏ、Ｎｉ及びＭｎからなる群から選択される少なくとも一種である。）で示されるリチウム酸化物を含む正極と、リチウムイオンを吸蔵放出可能な材料を含む負極とを備えるリチウムイオン電池の充電方法であって、リチウムイオン電池を充電する工程と、充電されたリチウムイオン電池について、電池全容量の０．１％以上を一部放電する工程と、一部放電されたリチウムイオン電池の開放起電力を測定する工程と、前記開放起電力から残存容量を算出する工程と、を含む。
[How to charge a lithium-ion battery]
The method for charging a lithium ion battery according to the present embodiment has a layered rock salt structure, and the following formula (1)
Li x M 1 y M 2 z O 2-d (1)
(In the formula (1), 1.16 ≦ x ≦ 1.32, 0.33 ≦ y ≦ 0.63, 0.06 ≦ z ≦ 0.50 and 0 ≦ d ≦ 0.20. M 1 Is at least one selected from the group consisting of Mn, Ti and Zr, and M 2 is at least one selected from the group consisting of Fe, Co, Ni and Mn.) A method for charging a lithium ion battery comprising a negative electrode containing a material capable of occluding and releasing lithium ions, the step of charging the lithium ion battery, and for the charged lithium ion battery, 0.1% or more of the total capacity of the battery Including a step of partially discharging, a step of measuring an open electromotive force of the partially discharged lithium ion battery, and a step of calculating a remaining capacity from the open electromotive force.
本実施形態に係るリチウムイオン電池の充電方法の各工程は、前記リチウムイオン電池の残存容量の測定方法と同様である。本実施形態に係るリチウムイオン電池の充電方法によれば、充電後の一部放電により残存容量は若干低減するものの、開放起電力から比較的簡単かつ正確に残存容量を測定することができる。 Each step of the method for charging a lithium ion battery according to this embodiment is the same as the method for measuring the remaining capacity of the lithium ion battery. According to the method for charging a lithium ion battery according to the present embodiment, although the remaining capacity is slightly reduced by partial discharge after charging, the remaining capacity can be measured relatively easily and accurately from the open electromotive force.
以下、具体的な実施例を用いて本実施形態を説明するが、本実施形態はこれらに限定されない。 Hereinafter, although this embodiment is described using a concrete example, this embodiment is not limited to these.
［実施例１］
＜正極作製＞
層状岩塩構造を有するリチウム酸化物Ｌｉ1.19Ｍｎ0.52Ｆｅ0.22Ｏ2を８５質量％、ケッチェンブラックを６質量％、気相成長炭素繊維を３質量％及びポリフッ化ビニリデンを６質量％含む混合物と、溶媒としてのＮメチルピロリドンとを含むインクを用意した。なお、該リチウム化合物が層状岩塩構造を有することは、粉末Ｘ線回折により確認した。以下の実施例、比較例についても同様である。該インクをアルミニウム箔（厚み２０μｍ）からなる正極集電体１Ａの片面に塗布して乾燥し、正極集電体１Ａ上に厚み３５μｍの正極１を作製した。正極集電体１Ａの両面に該インクを塗布して乾燥させた両面電極も同様に作製した。
[Example 1]
<Positive electrode fabrication>
A mixture containing 85% by mass of lithium oxide Li 1.19 Mn 0.52 Fe 0.22 O 2 having a layered rock salt structure, 6% by mass of ketjen black, 3% by mass of vapor-grown carbon fiber and 6% by mass of polyvinylidene fluoride; An ink containing N-methylpyrrolidone as a solvent was prepared. It was confirmed by powder X-ray diffraction that the lithium compound had a layered rock salt structure. The same applies to the following examples and comparative examples. The ink was applied to one side of a positive electrode current collector 1A made of an aluminum foil (thickness 20 μm) and dried to produce a positive electrode 1 having a thickness of 35 μm on the positive electrode current collector 1A. A double-sided electrode in which the ink was applied to both sides of the positive electrode current collector 1A and dried was similarly produced.
＜負極作製＞
平均粒径１５μｍの人造黒鉛を９０質量％、ケッチェンブラックを１質量％及びポリフッ化ビニリデンを９質量％含む混合物と、溶媒としてのＮメチルピロリドンとを含むインクを用意した。該インクを銅箔（厚み１０μｍ）からなる負極集電体２Ａの片面に塗布して乾燥し、負極集電体２Ａ上に厚み４８μｍの負極２を作製した。負極集電体２Ａの両面に該インクを塗布して乾燥させた両面電極も同様に作製した。
<Negative electrode production>
An ink containing 90% by mass of artificial graphite having an average particle size of 15 μm, 1% by mass of ketjen black and 9% by mass of polyvinylidene fluoride and N-methylpyrrolidone as a solvent was prepared. The ink was applied to one side of a negative electrode current collector 2A made of copper foil (thickness 10 μm) and dried to prepare a negative electrode 2 having a thickness of 48 μm on the negative electrode current collector 2A. A double-sided electrode in which the ink was applied to both sides of the negative electrode current collector 2A and dried was similarly produced.
＜電解液作製＞
カーボネート（ＥＣ）／ジエチルカーボネート（ＤＥＣ）を３／７（体積比）で混合した。この混合液にＬｉＰＦ6を溶解させて電解液を作製した。電解液中のＬｉＰＦ6の濃度は１ｍｏｌ／ｌであった。
<Electrolyte preparation>
Carbonate (EC) / diethyl carbonate (DEC) was mixed at 3/7 (volume ratio). LiPF 6 was dissolved in this mixed solution to prepare an electrolytic solution. The concentration of LiPF 6 in the electrolytic solution was 1 mol / l.
＜リチウムイオン電池作製＞
前記方法で作製した正極１、正極集電体１Ａ、負極２及び負極集電体２Ａを、多孔質フィルムセパレータ３を介して積層した。正極集電体１Ａに正極タブ１Ｂを、負極集電体２Ａに負極タブ２Ｂを溶接することで発電要素を作製した。該発電要素をアルミラミネートフィルムからなる外装体４で包み、３辺を熱融着により封止した。その後、該発電要素に前記方法で作製した電解質を適度な真空度にて含浸させた。減圧下にて残りの１辺を熱融着して封止し、リチウムイオン電池を作製した。
<Production of lithium ion battery>
The positive electrode 1, the positive electrode current collector 1 </ b> A, the negative electrode 2, and the negative electrode current collector 2 </ b> A produced by the above method were laminated via a porous film separator 3. A power generation element was fabricated by welding the positive electrode tab 1B to the positive electrode current collector 1A and the negative electrode tab 2B to the negative electrode current collector 2A. The power generation element was wrapped with an outer package 4 made of an aluminum laminate film, and three sides were sealed by heat sealing. Thereafter, the power generation element was impregnated with the electrolyte produced by the above method at an appropriate degree of vacuum. The remaining one side was heat-sealed and sealed under reduced pressure to produce a lithium ion battery.
＜酸化処理工程＞
作製したリチウムイオン電池について、２０ｍＡ／ｇの電流で４．２Ｖまで充電し、２０ｍＡ／ｇの電流で２．０Ｖまで放電した。次のサイクル以降は上限電圧を０．１Ｖずつ上昇させた。すなわち、次のサイクルでは４．３Ｖまで充電して２．０Ｖまで放電し、その次のサイクルでは４．４Ｖまで充電して２．０Ｖまで放電した。最終的に上限電圧が４．８Ｖになるまで７サイクルを繰り返すことで、リチウムイオン電池の電気化学的な酸化処理を行った。その後、一旦封口部を破り減圧することで電池内部のガスを抜き、再度封口した。得られたリチウムイオン電池の電池全容量は２４０ｍＡｈ／ｇであった。電池全容量は１０ｍＡ／ｇでの定電流充放電により求めた。
<Oxidation process>
About the produced lithium ion battery, it charged to 4.2V with the electric current of 20 mA / g, and discharged to 2.0V with the electric current of 20 mA / g. After the next cycle, the upper limit voltage was increased by 0.1V. That is, in the next cycle, the battery was charged to 4.3 V and discharged to 2.0 V, and in the next cycle, the battery was charged to 4.4 V and discharged to 2.0 V. The electrochemical process of the lithium ion battery was performed by repeating 7 cycles until the upper limit voltage finally reached 4.8V. Thereafter, the sealing portion was once broken and the pressure was reduced, thereby removing the gas inside the battery and sealing again. The total capacity of the obtained lithium ion battery was 240 mAh / g. The total battery capacity was determined by constant current charge / discharge at 10 mA / g.
＜充電工程及び一部放電工程＞
前記方法で作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で１００ｍＡｈ／ｇ（２時間３０分間）充電した。その直後に４０ｍＡ／ｇの電流で１０ｍＡｈ／ｇ（１５分間）放電した。
<Charging process and partial discharge process>
The lithium ion battery (2.0 V discharge state) produced by the above method was charged with 100 mAh / g (2 hours 30 minutes) at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 10 mAh / g (15 minutes) was discharged at a current of 40 mA / g.
＜開放起電力測定工程＞
充電及び一部放電を行ったリチウムイオン電池を開回路状態で１時間放置し、開放起電力を測定した。
<Open electromotive force measurement process>
The lithium ion battery that had been charged and partially discharged was left in an open circuit state for 1 hour, and the open electromotive force was measured.
＜残存容量算出工程＞
前記開放起電力を用い、放電曲線の形状より残存容量を算出した。結果を表１に示す。
<Remaining capacity calculation process>
Using the open electromotive force, the remaining capacity was calculated from the shape of the discharge curve. The results are shown in Table 1.
［実施例２］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で９２．４ｍＡｈ／ｇ充電した。その直後に４０ｍＡ／ｇの電流で２．４ｍＡｈ／ｇ放電した。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 2]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 92.4 mAh / g at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 2.4 mAh / g was discharged at a current of 40 mA / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例３］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で１１４ｍＡｈ／ｇ充電した。その直後に４０ｍＡ／ｇの電流で２４ｍＡｈ／ｇ放電した。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 3]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 114 mAh / g at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 24 mAh / g was discharged at a current of 40 mA / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例４］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で１３８ｍＡｈ／ｇ充電した。その直後に４０ｍＡ／ｇの電流で４８ｍＡｈ／ｇ放電した。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 4]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 138 mAh / g at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 48 mAh / g was discharged at a current of 40 mA / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例５］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で４．８Ｖ（定電圧充電で５ｍＡｈ／ｇ）まで充電して満充電状態にした。その直後に４０ｍＡ／ｇの電流で放電して実残存容量を９０ｍＡｈ／ｇとした。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 5]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged to 4.8 V (5 mAh / g by constant voltage charging) at a current of 40 mA / g per positive electrode active material to be fully charged. . Immediately thereafter, the battery was discharged at a current of 40 mA / g, so that the actual remaining capacity was 90 mAh / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例６］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で４０ｍＡｈ／ｇ充電した。その直後に４０ｍＡ／ｇの電流で１０ｍＡｈ／ｇ放電した。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 6]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged with 40 mAh / g at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 10 mAh / g was discharged at a current of 40 mA / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例７］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で４．８Ｖ（定電圧充電で５ｍＡｈ／ｇ）まで充電して満充電状態にした。その直後に４０ｍＡ／ｇの電流で放電して実残存容量を３０ｍＡｈ／ｇにした。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 7]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged to 4.8 V (5 mAh / g by constant voltage charging) at a current of 40 mA / g per positive electrode active material to be fully charged. . Immediately thereafter, the battery was discharged at a current of 40 mA / g to make the actual remaining capacity 30 mAh / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例８］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で１９０ｍＡｈ／ｇ充電した。その直後に４０ｍＡ／ｇの電流で１０ｍＡｈ／ｇ放電した。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 8]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 190 mAh / g at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 10 mAh / g was discharged at a current of 40 mA / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例９］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で４．８Ｖ（定電圧充電で５ｍＡｈ／ｇ）まで充電して満充電状態にした。その直後に４０ｍＡ／ｇの電流で放電して実残存容量を１８０ｍＡｈ／ｇにした。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 9]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged to 4.8 V (5 mAh / g by constant voltage charging) at a current of 40 mA / g per positive electrode active material to be fully charged. . Immediately after that, the battery was discharged at a current of 40 mA / g to make the actual remaining capacity 180 mAh / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例１０］
正極活物質として、層状岩塩構造を有するリチウム酸化物Ｌｉ1.19Ｍｎ0.52Ｆｅ0.22Ｏ2の代わりに、層状岩塩構造を有するリチウム酸化物Ｌｉ1.2Ｍｎ0.4Ｎｉ0.4Ｏ2を用いた以外は実施例１と同様にリチウムイオン電池を作製した。なお、該リチウムイオン電池の電池全容量は２６２ｍＡｈ／ｇであった。該リチウムイオン電池を正極活物質あたり４０ｍＡ／ｇの電流で１００ｍＡｈ／ｇ（２時間３０分間）充電した。その直後に４０ｍＡ／ｇの電流で１０ｍＡｈ／ｇ（１５分間）放電した。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 10]
Example 1 except that lithium oxide Li 1.2 Mn 0.4 Ni 0.4 O 2 having a layered rock salt structure was used as the positive electrode active material instead of lithium oxide Li 1.19 Mn 0.52 Fe 0.22 O 2 having a layered rock salt structure Similarly, a lithium ion battery was produced. The total battery capacity of the lithium ion battery was 262 mAh / g. The lithium ion battery was charged at 100 mAh / g (2 hours 30 minutes) at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 10 mAh / g (15 minutes) was discharged at a current of 40 mA / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［実施例１１］
実施例１０と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で４．８Ｖ（定電圧充電で５ｍＡｈ／ｇ）まで充電して満充電状態にした。その直後に４０ｍＡ／ｇの電流で放電して実残存容量を９０ｍＡｈ／ｇにした。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Example 11]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 10 was charged to 4.8 V (5 mAh / g by constant voltage charging) at a current of 40 mA / g per positive electrode active material to be fully charged. . Immediately thereafter, the battery was discharged at a current of 40 mA / g to make the actual remaining capacity 90 mAh / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［比較例１］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で９０ｍＡｈ／ｇ充電し、一部放電は行わなかった。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Comparative Example 1]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 90 mAh / g at a current of 40 mA / g per positive electrode active material, and partial discharge was not performed. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［比較例２］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で９０．１ｍＡｈ／ｇ充電した。その直後に４０ｍＡ／ｇの電流で０．１ｍＡｈ／ｇ放電した。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Comparative Example 2]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 90.1 mAh / g at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 0.1 mAh / g was discharged at a current of 40 mA / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［比較例３］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で９０．２ｍＡｈ／ｇ充電した。その直後に４０ｍＡ／ｇの電流で０．２ｍＡｈ／ｇ放電した。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Comparative Example 3]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 90.2 mAh / g at a current of 40 mA / g per positive electrode active material. Immediately thereafter, 0.2 mAh / g was discharged at a current of 40 mA / g. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［比較例４］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で３０ｍＡｈ／ｇ充電し、一部放電は行わなかった。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Comparative Example 4]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 30 mAh / g at a current of 40 mA / g per positive electrode active material, and partial discharge was not performed. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［比較例５］
実施例１と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で１８０ｍＡｈ／ｇ充電し、一部放電は行わなかった。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Comparative Example 5]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 1 was charged at 180 mAh / g at a current of 40 mA / g per positive electrode active material, and partial discharge was not performed. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
［比較例６］
実施例１０と同様に作製したリチウムイオン電池（２．０Ｖ放電状態）を正極活物質あたり４０ｍＡ／ｇの電流で９０ｍＡｈ／ｇ充電し、一部放電は行わなかった。その後、実施例１と同様に開放起電力の測定及び残存容量の算出を行った。結果を表１に示す。
[Comparative Example 6]
A lithium ion battery (2.0 V discharge state) produced in the same manner as in Example 10 was charged at 90 mAh / g at a current of 40 mA / g per positive electrode active material, and partial discharge was not performed. Thereafter, the open electromotive force was measured and the remaining capacity was calculated in the same manner as in Example 1. The results are shown in Table 1.
＜リチウムイオン電池の評価結果＞
正極活物質として層状岩塩構造を有するリチウム酸化物Ｌｉ1.19Ｍｎ0.52Ｆｅ0.22Ｏ2を使用したリチウムイオン電池において、充電後、電池全容量の０．１％以上を一部放電することで実残存容量を９０ｍＡｈ／ｇとした実施例１から５では、互いに開放起電力の差が小さく、実残存容量の値に近い算出残存容量が得られた。したがって、比較的簡単かつ正確に開放起電力から残存容量を測定することができた。一方、充電後、一部放電を行わない、又は電池全容量の０．１％未満を一部放電して実残存容量を９０ｍＡｈ／ｇとした比較例１から３では、開放起電力がそれぞれ３．８９Ｖ、３．６４Ｖ及び３．５４Ｖであり、実施例１から５の開放起電力の値と大きく異なった。また、実残存容量の値と算出残存容量の値に大きな差があった。
<Evaluation results of lithium ion battery>
In a lithium ion battery using a lithium oxide Li 1.19 Mn 0.52 Fe 0.22 O 2 having a layered rock salt structure as the positive electrode active material, after charging, the actual remaining capacity is partially discharged by 0.1% or more of the total capacity of the battery In Examples 1 to 5 in which the value was 90 mAh / g, the difference in open electromotive force was small and a calculated remaining capacity close to the value of the actual remaining capacity was obtained. Therefore, the remaining capacity could be measured from the open electromotive force relatively easily and accurately. On the other hand, in Comparative Examples 1 to 3 in which partial discharge was not performed after charging or less than 0.1% of the total battery capacity was partially discharged and the actual remaining capacity was 90 mAh / g, the open electromotive force was 3 respectively. .89V, 3.64V, and 3.54V, which were significantly different from the open electromotive force values of Examples 1 to 5. There was also a large difference between the value of the actual remaining capacity and the calculated remaining capacity.
正極活物質として層状岩塩構造を有するリチウム酸化物Ｌｉ1.19Ｍｎ0.52Ｆｅ0.22Ｏ2を使用したリチウムイオン電池において、充電後、電池全容量の０．１％以上を一部放電することで実残存容量を３０ｍＡｈ／ｇとした実施例６及び７では、互いに開放起電力の差が小さく、実残存容量の値に近い算出残存容量が得られた。したがって、比較的簡単かつ正確に開放起電力から残存容量を測定することができた。一方、充電後、一部放電を行わずに実残存容量を３０ｍＡｈ／ｇとした比較例４では、開放起電力が３．５２Ｖであり、実施例６及び７の開放起電力の値と大きく異なった。また、実残存容量の値と算出残存容量の値に大きな差があった。 In a lithium ion battery using a lithium oxide Li 1.19 Mn 0.52 Fe 0.22 O 2 having a layered rock salt structure as the positive electrode active material, after charging, the actual remaining capacity is partially discharged by 0.1% or more of the total capacity of the battery In Examples 6 and 7 in which the value was 30 mAh / g, the difference in open electromotive force was small, and a calculated remaining capacity close to the value of the actual remaining capacity was obtained. Therefore, the remaining capacity could be measured from the open electromotive force relatively easily and accurately. On the other hand, in Comparative Example 4 in which the actual remaining capacity was 30 mAh / g without partial discharge after charging, the open electromotive force was 3.52 V, which was significantly different from the open electromotive force values of Examples 6 and 7. It was. There was also a large difference between the value of the actual remaining capacity and the calculated remaining capacity.
正極活物質として層状岩塩構造を有するリチウム酸化物Ｌｉ1.19Ｍｎ0.52Ｆｅ0.22Ｏ2を使用したリチウムイオン電池において、充電後、電池全容量の０．１％以上を一部放電することで実残存容量を１８０ｍＡｈ／ｇとした実施例８及び９では、互いに開放起電力の差が小さく、実残存容量の値に近い算出残存容量が得られた。したがって、比較的簡単かつ正確に開放起電力から残存容量を測定することができた。一方、充電後、一部放電を行わずに実残存容量を１８０ｍＡｈ／ｇとした比較例５では、開放起電力が４．４７Ｖであり、実施例８及び９の開放起電力の値と大きく異なった。また、実残存容量の値と算出残存容量の値に大きな差があった。 In a lithium ion battery using a lithium oxide Li 1.19 Mn 0.52 Fe 0.22 O 2 having a layered rock salt structure as the positive electrode active material, after charging, the actual remaining capacity is partially discharged by 0.1% or more of the total capacity of the battery In Examples 8 and 9, in which the value was 180 mAh / g, the difference in open electromotive force was small, and a calculated remaining capacity close to the value of the actual remaining capacity was obtained. Therefore, the remaining capacity could be measured from the open electromotive force relatively easily and accurately. On the other hand, in Comparative Example 5 in which the actual remaining capacity was 180 mAh / g without partial discharge after charging, the open electromotive force was 4.47 V, which is significantly different from the open electromotive force values of Examples 8 and 9. It was. There was also a large difference between the value of the actual remaining capacity and the calculated remaining capacity.
正極活物質として層状岩塩構造を有するリチウム酸化物Ｌｉ1.2Ｍｎ0.4Ｎｉ0.4Ｏ2を使用したリチウムイオン電池において、充電後、電池全容量の０．１％以上を一部放電することで実残存容量を９０ｍＡｈ／ｇとした実施例１０及び１１では、互いに開放起電力の差が小さく、実残存容量の値に近い算出残存容量が得られた。したがって、比較的簡単かつ正確に開放起電力から残存容量を測定することができた。一方、充電後、一部放電を行わずに実残存容量を９０ｍＡｈ／ｇとした比較例６では、開放起電力が３．６９Ｖであり、実施例１０及び１１の開放起電力の値と大きく異なった。また、実残存容量の値と算出残存容量の値に大きな差があった。 In a lithium ion battery using a lithium oxide Li 1.2 Mn 0.4 Ni 0.4 O 2 having a layered rock salt structure as a positive electrode active material, the actual remaining capacity is obtained by partially discharging 0.1% or more of the total capacity of the battery after charging. In Examples 10 and 11 in which the value was 90 mAh / g, the difference in open electromotive force was small, and a calculated remaining capacity close to the value of the actual remaining capacity was obtained. Therefore, the remaining capacity could be measured from the open electromotive force relatively easily and accurately. On the other hand, in Comparative Example 6 in which the actual remaining capacity was 90 mAh / g without partial discharge after charging, the open electromotive force was 3.69 V, which is significantly different from the open electromotive force values of Examples 10 and 11. It was. There was also a large difference between the value of the actual remaining capacity and the calculated remaining capacity.
本実施形態に係るリチウムイオン電池の残存容量の測定方法によれば、残存容量を簡単かつ正確に評価することができるため、該方法を電子機器、電気自動車、一般家庭又は施設の電力貯蔵用蓄電池等に用いた場合、利便性が向上する。 According to the method for measuring the remaining capacity of the lithium ion battery according to the present embodiment, the remaining capacity can be easily and accurately evaluated. When it is used, etc., convenience is improved.
１ 正極
１Ａ 正極集電体
１Ｂ 正極タブ
２ 負極
２Ａ 負極集電体
２Ｂ 負極タブ
３ セパレータ
４ 外装体
１０ リチウムイオン電池
１１ 充電手段
１２ 一部放電手段
１３ 開放起電力測定手段
１４ 残存容量算出手段
DESCRIPTION OF SYMBOLS 1 Positive electrode 1A Positive electrode collector 1B Positive electrode tab 2 Negative electrode 2A Negative electrode collector 2B Negative electrode tab 3 Separator 4 Outer body 10 Lithium ion battery 11 Charging means 12 Partial discharge means 13 Open electromotive force measurement means 14 Residual capacity calculation means
Claims (5)
ＬｉｘＭ１ ｙＭ２ ｚＯ２−ｄ （１）
（前記式（１）において、１．１６≦ｘ≦１．３２、０．３３≦ｙ≦０．６３、０．０６≦ｚ≦０．３１及び０≦ｄ≦０．２０である。Ｍ１はＭｎ、Ｔｉ及びＺｒからなる群から選択される少なくとも一種、Ｍ２はＦｅ、Ｃｏ、Ｎｉ及びＭｎからなる群から選択される少なくとも一種である。）
で示されるリチウム酸化物を含む正極と、リチウムイオンを吸蔵放出可能な材料を含む負極とを備えるリチウムイオン電池の残存容量の測定方法であって、
リチウムイオン電池を充電する工程と、
充電されたリチウムイオン電池について、電池全容量の０．１％以上を一部放電する工程と、
一部放電されたリチウムイオン電池の開放起電力を測定する工程と、
前記開放起電力から残存容量を算出する工程と、
を含むリチウムイオン電池の残存容量の測定方法。 The following formula (1) having a layered rock salt structure
Li x M 1 y M 2 z O 2-d (1)
(In the formula (1), 1.16 ≦ x ≦ 1.32, 0.33 ≦ y ≦ 0.63, 0.06 ≦ z ≦ 0.31 and 0 ≦ d ≦ 0.20. M 1 the Mn, at least one selected from the group consisting of Ti and Zr, M 2 is at least one selected from the group consisting of Fe, Co, Ni and Mn.)
A method for measuring the remaining capacity of a lithium ion battery comprising a positive electrode containing lithium oxide and a negative electrode containing a material capable of occluding and releasing lithium ions,
Charging the lithium ion battery;
For a charged lithium ion battery, a step of partially discharging 0.1% or more of the total battery capacity;
Measuring the open electromotive force of a partially discharged lithium ion battery;
Calculating a remaining capacity from the open electromotive force;
Of the remaining capacity of a lithium ion battery including
ＬｉｘＭ１ ｙＭ２ ｚＯ２−ｄ （１）
（前記式（１）において、１．１６≦ｘ≦１．３２、０．３３≦ｙ≦０．６３、０．０６≦ｚ≦０．３１及び０≦ｄ≦０．２０である。Ｍ１はＭｎ、Ｔｉ及びＺｒからなる群から選択される少なくとも一種、Ｍ２はＦｅ、Ｃｏ、Ｎｉ及びＭｎからなる群から選択される少なくとも一種である。）
で示されるリチウム酸化物を含む正極と、リチウムイオンを吸蔵放出可能な材料を含む負極とを備えるリチウムイオン電池と、
前記リチウムイオン電池を充電する手段と、
前記リチウムイオン電池を充電する手段により充電されたリチウムイオン電池について、電池全容量の０．１％以上を一部放電する手段と、
前記リチウムイオン電池を一部放電する手段により一部放電されたリチウムイオン電池の開放起電力を測定する手段と、
前記開放起電力を測定する手段により測定された開放起電力から残存容量を算出する手段と、
を備える蓄電システム。 The following formula (1) having a layered rock salt structure
Li x M 1 y M 2 z O 2-d (1)
(In the formula (1), 1.16 ≦ x ≦ 1.32, 0.33 ≦ y ≦ 0.63, 0.06 ≦ z ≦ 0.31 and 0 ≦ d ≦ 0.20. M 1 the Mn, at least one selected from the group consisting of Ti and Zr, M 2 is at least one selected from the group consisting of Fe, Co, Ni and Mn.)
A lithium ion battery comprising: a positive electrode comprising a lithium oxide represented by: a negative electrode comprising a material capable of occluding and releasing lithium ions;
Means for charging the lithium ion battery;
For the lithium ion battery charged by the means for charging the lithium ion battery, means for partially discharging 0.1% or more of the total battery capacity;
Means for measuring an open electromotive force of a lithium ion battery partially discharged by means for partially discharging the lithium ion battery;
Means for calculating a remaining capacity from the open electromotive force measured by the means for measuring the open electromotive force;
A power storage system comprising:
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