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JP5101068B2 - Negative electrode material for non-aqueous secondary battery and non-aqueous secondary battery using the same - Google Patents
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JP5101068B2 - Negative electrode material for non-aqueous secondary battery and non-aqueous secondary battery using the same - Google Patents

Negative electrode material for non-aqueous secondary battery and non-aqueous secondary battery using the same Download PDF

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JP5101068B2
JP5101068B2 JP2006252225A JP2006252225A JP5101068B2 JP 5101068 B2 JP5101068 B2 JP 5101068B2 JP 2006252225 A JP2006252225 A JP 2006252225A JP 2006252225 A JP2006252225 A JP 2006252225A JP 5101068 B2 JP5101068 B2 JP 5101068B2
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徹 稲垣
小池　　将樹
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Electrochemistry (AREA)
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Description

本発明は、リチウムイオン二次電池等の非水二次電池及びその負極材料に関する。   The present invention relates to a nonaqueous secondary battery such as a lithium ion secondary battery and a negative electrode material thereof.

従来の非水二次電池は特許文献１に開示されている。この非水二次電池は非水系の電解質内にリチウムイオンを吸蔵及び脱離できる正極及び負極が浸漬される。負極材料はリチウムバナジウム酸化物から成っている。このリチウムバナジウム酸化物は水酸化リチウム等のリチウム供給源と三酸化バナジウム等のバナジウム供給源とを固相法により混合し、６５０℃以上で焼成して形成される。   A conventional non-aqueous secondary battery is disclosed in Patent Document 1. In this non-aqueous secondary battery, a positive electrode and a negative electrode capable of inserting and extracting lithium ions are immersed in a non-aqueous electrolyte. The negative electrode material is made of lithium vanadium oxide. The lithium vanadium oxide is formed by mixing a lithium supply source such as lithium hydroxide and a vanadium supply source such as vanadium trioxide by a solid phase method and firing at 650 ° C. or higher.

非水二次電池の充電時には負極が負に帯電し、正極に吸蔵されたリチウムイオンが脱離して負極に吸蔵される。非水二次電池の放電時には負極に吸蔵されたリチウムイオンが脱離して正極に吸蔵される。これにより、負極での金属リチウムの析出を防止して寿命の長い非水二次電池を得ることができる。
特開２００３−６８３０５号公報（第３頁−第１１頁、第１０図） When the non-aqueous secondary battery is charged, the negative electrode is negatively charged, and lithium ions stored in the positive electrode are desorbed and stored in the negative electrode. At the time of discharging the non-aqueous secondary battery, lithium ions stored in the negative electrode are desorbed and stored in the positive electrode. Thereby, precipitation of metallic lithium at the negative electrode can be prevented, and a non-aqueous secondary battery having a long life can be obtained.
Japanese Patent Laid-Open No. 2003-68305 (page 3 to page 11, FIG. 10)

非水二次電池はノート型パーソナルコンピュータや携帯電話機等の可搬性の電子機器に広く用いられ、電子機器の消費電力が大きくなっても満充電からの稼働時間を長く維持できることが望まれる。このため、より大きな放電容量が得られる非水二次電池が求められている。   Non-aqueous secondary batteries are widely used in portable electronic devices such as notebook personal computers and mobile phones, and it is desired that the operation time from full charge can be maintained long even when the power consumption of the electronic devices increases. For this reason, a non-aqueous secondary battery capable of obtaining a larger discharge capacity is demanded.

本発明は、放電容量を向上できる非水二次電池及びそれを用いた非水二次電池用負極材料を提供することを目的とする。   An object of this invention is to provide the non-aqueous secondary battery which can improve discharge capacity, and the negative electrode material for non-aqueous secondary batteries using the same.

上記目的を達成するために本発明は、リチウムバナジウム酸化物を主成分とした負極活物質として用いられる非水二次電池用負極材料において、前記負極活物質は０．５重量％以上３．０重量％以下のＬｉ3ＶＯ4が含まれることを特徴としている。この構成によると、負極活物質として用いられる非水二次電池用負極材料はＬｉＶＯ2やＬｉ3ＶＯ4等のリチウムバナジウム酸化物により形成され、Ｌｉ3ＶＯ4の含有量が０．５重量％以上３．０重量％以下になっている。 In order to achieve the above object, the present invention provides a negative electrode material for a non-aqueous secondary battery used as a negative electrode active material mainly composed of lithium vanadium oxide, wherein the negative electrode active material is 0.5 wt% or more and 3.0 It is characterized by containing Li 3 VO 4 in an amount of not more than% by weight. According to this configuration, the negative electrode material for a non-aqueous secondary battery used as the negative electrode active material is formed of lithium vanadium oxide such as LiVO 2 or Li 3 VO 4, and the content of Li 3 VO 4 is 0.5% by weight. It is more than 3.0 weight% above.

また本発明は、上記構成の非水二次電池用負極材料において、前記負極活物質は０．５重量％以下のバナジウム炭化物が含まれることを特徴としている。   According to the present invention, in the negative electrode material for a non-aqueous secondary battery having the above-described configuration, the negative electrode active material contains 0.5% by weight or less of vanadium carbide.

また本発明は、上記構成の非水二次電池用負極材料において、前記負極活物質の平均粒径が１０μｍ以上５０μｍ以下であることを特徴としている。   According to the present invention, in the negative electrode material for a non-aqueous secondary battery configured as described above, the negative electrode active material has an average particle size of 10 μm or more and 50 μm or less.

また本発明は、リチウムバナジウム酸化物を主成分とした負極活物質として用いられる非水二次電池用負極材料において、前記負極活物質は０．５重量％以下のバナジウム炭化物が含まれることを特徴としている。   Further, the present invention provides a negative electrode material for a non-aqueous secondary battery used as a negative electrode active material mainly composed of lithium vanadium oxide, wherein the negative electrode active material contains 0.5% by weight or less of vanadium carbide. It is said.

また本発明の非水二次電池は、上記各構成の非水二次電池用負極材料から成る負極と、正極と、電解質とから成ることを特徴としている。   The non-aqueous secondary battery of the present invention is characterized by comprising a negative electrode made of a negative electrode material for a non-aqueous secondary battery having the above-described configuration, a positive electrode, and an electrolyte.

本発明によると、リチウムバナジウム酸化物を主成分とする負極活物質が０．５重量％以上３．０重量％以下のＬｉ3ＶＯ4を含むので、非水二次電池の放電容量を向上することができる。 According to the present invention, the negative electrode active material mainly composed of lithium vanadium oxide contains 0.5 wt% or more and 3.0 wt% or less of Li 3 VO 4 , thereby improving the discharge capacity of the non-aqueous secondary battery. be able to.

以下に本発明の実施形態を図面を参照して説明する。図１は一実施形態の非水二次電池を示す縦断面図である。非水二次電池１はスパイラル式円筒型のリチウム二次電池から成る。非水二次電池１にはセンターピン６が設けられ、正極３と負極４との間にセパレータ５が挟まれて成る積層体１０がセンターピン６に多重に巻かれている。これにより、積層体１０は円筒状構造を成している。   Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a longitudinal sectional view showing a nonaqueous secondary battery according to an embodiment. The non-aqueous secondary battery 1 is composed of a spiral cylindrical lithium secondary battery. The non-aqueous secondary battery 1 is provided with a center pin 6, and a laminate 10 in which a separator 5 is sandwiched between a positive electrode 3 and a negative electrode 4 is wound around the center pin 6 in a multiple manner. Thereby, the laminated body 10 has comprised the cylindrical structure.

正極３は正極活物質を含む正極合材３ａにより正極集電体３ｂの表面及び裏面の２層を挟んで形成される。負極４は負極活物質を含む負極合材４ａにより負極集電体４ｂの表面及び裏面の２層を挟んで形成される。円筒状の積層体１０は中空円柱状のケース２内に収納され、電解質（不図示）に浸漬されている。ケース２によって正極３が接続されるとともに下端が突出した正極端子７が形成されている。   The positive electrode 3 is formed by sandwiching two layers of the front surface and the back surface of the positive electrode current collector 3b with a positive electrode mixture 3a containing a positive electrode active material. The negative electrode 4 is formed by sandwiching two layers of the front surface and the back surface of the negative electrode current collector 4b with a negative electrode mixture 4a containing a negative electrode active material. The cylindrical laminate 10 is housed in a hollow cylindrical case 2 and is immersed in an electrolyte (not shown). A positive electrode 3 is connected by the case 2 and a positive electrode terminal 7 having a lower end protruding is formed.

積層体１０の上下にはそれぞれ絶縁板９ｂ、９ａが設けられる。正極集電体３ｂは、絶縁板９ａを貫通して正極リード１１により正極端子７に接続されている。ケース２の開口側の絶縁板９ｂ上には、絶縁板９ｂ方向に凸形状を有する安全弁１３が設けられる。安全弁１３の上方には、安全弁１３とは反対方向に凸形状を有するキャップ状の負極端子８が形成されている。負極集電体４ｂは絶縁板９ｂを貫通して負極リード１２により負極端子８に接続されている。また、安全弁１３及び負極端子８の縁面はガスケット１４によりシールされ、正極端子７から離間している。   Insulating plates 9b and 9a are provided above and below the laminate 10, respectively. The positive electrode current collector 3 b passes through the insulating plate 9 a and is connected to the positive electrode terminal 7 by the positive electrode lead 11. On the insulating plate 9b on the opening side of the case 2, a safety valve 13 having a convex shape in the direction of the insulating plate 9b is provided. A cap-like negative electrode terminal 8 having a convex shape in the opposite direction to the safety valve 13 is formed above the safety valve 13. The negative electrode current collector 4 b passes through the insulating plate 9 b and is connected to the negative electrode terminal 8 by the negative electrode lead 12. Further, the edge surfaces of the safety valve 13 and the negative electrode terminal 8 are sealed by the gasket 14 and are separated from the positive electrode terminal 7.

正極活物質及び電解質には非水二次電池の正極及び電解質として公知の材料が用いられる。例えば、正極活物質にはコバルト酸リチウム等のリチウム遷移金属酸化物が用いられる。また、電解質には炭酸エチレンや炭酸ジエチル等の溶媒に、ＬｉＰＦ6、Ｌｉ2ＳｉＦ6、Ｌｉ2ＴｉＦ6、ＬｉＢＦ4等のリチウム塩から成る溶質を含有したものが用いられる。 As the positive electrode active material and the electrolyte, materials known as positive electrodes and electrolytes of non-aqueous secondary batteries are used. For example, a lithium transition metal oxide such as lithium cobalt oxide is used for the positive electrode active material. As the electrolyte, an electrolyte containing a solvent such as ethylene carbonate or diethyl carbonate and a solute composed of a lithium salt such as LiPF 6 , Li 2 SiF 6 , Li 2 TiF 6 , LiBF 4 is used.

負極４はリチウムバナジウム酸化物を主成分とする負極活物質を有している。そして、リチウムバナジウム酸化物８０重量％、アセチレンブラック１０重量％、バインダー１０重量％を混合して銅集電体上に塗布し、１．８ｇ／ｃｍ3となるようにプレス加工して形成されている。 The negative electrode 4 has a negative electrode active material mainly composed of lithium vanadium oxide. Then, 80% by weight of lithium vanadium oxide, 10% by weight of acetylene black, and 10% by weight of a binder are mixed and applied onto a copper current collector, and formed by pressing to obtain 1.8 g / cm 3. Yes.

本実施形態においては、上記負極活物質に通常では不純物と考えられるＬｉ3ＶＯ4及び／又はバナジウム炭化物（ＶＣ）を含有させている。Ｌｉ3ＶＯ4は、主成分であるリチウムバナジウム酸化物（ＬｉＶＯ2）と比較して、融点が低い（６００℃程度）。このため、負極活物質を焼成により得る際に、主成分であるＬｉＶＯ2の粒子同士の結合を促進することができると考えられる。Ｌｉ3ＶＯ4の混合量が増加するにしたがって、平均粒径も増大する。 In the present embodiment, the negative electrode active material contains Li 3 VO 4 and / or vanadium carbide (VC) which are normally considered as impurities. Li 3 VO 4 has a lower melting point (about 600 ° C.) than lithium vanadium oxide (LiVO 2 ), which is the main component. Therefore, when obtaining by sintering a negative electrode active material, it is considered possible to promote the binding of particles of the LiVO 2 is a main component. As the mixing amount of Li 3 VO 4 increases, the average particle size also increases.

Ｌｉ3ＶＯ4の含有量は、０．５重量％〜３．０重量％が最適であると考えられ、平均粒径は、１０μｍ〜５０μｍが最適であると考えられる。平均粒径が小さすぎると、負極活物質と導電材とを混合させたときに負極活物質が導電材と接触する確率が低下するため好ましくない。一方で、Ｌｉ3ＶＯ4の量が増大すると粒径は高まるものの、負極活物質としては不純物であるＬｉ3ＶＯ4の量が増大することにより、放電容量が減るため好ましくない。 The optimal content of Li 3 VO 4 is considered to be 0.5% by weight to 3.0% by weight, and the average particle size is considered to be optimal from 10 μm to 50 μm. If the average particle size is too small, the probability that the negative electrode active material contacts the conductive material when the negative electrode active material and the conductive material are mixed is not preferable. On the other hand, when the amount of Li 3 VO 4 increases, the particle size increases. However, as the amount of Li 3 VO 4 that is an impurity increases as the negative electrode active material, the discharge capacity decreases, which is not preferable.

一方、ＶＣを負極活物質内に含有させた場合には、ＶＣが体積抵抗率１５０×１０-6Ω・ｃｍの良導体であるために粒子内の導電性が向上し、例えば３ｍＡ／ｃｍ2の高効率放電にも対応可能な負極活物質が得られると考えられる。しかしながら、ＶＣはリチウムの吸蔵を担うリチウムバナジウム酸化物のバナジウムを過剰に奪ってしまい放電容量を低下させる。このため、ＶＣの含有量は０．５重量％以下とすることが好ましい。 On the other hand, when VC is contained in the negative electrode active material, since VC is a good conductor having a volume resistivity of 150 × 10 −6 Ω · cm, the conductivity in the particles is improved, for example, 3 mA / cm 2 . It is considered that a negative electrode active material that can cope with high-efficiency discharge can be obtained. However, VC deprives vanadium of the lithium vanadium oxide, which is responsible for occlusion of lithium, and reduces the discharge capacity. For this reason, the content of VC is preferably 0.5% by weight or less.

次に、本発明の実施例について説明する。実施例１の負極活物質の試料はＬｉＯＨ（水酸化リチウム）とＶ2Ｏ3（三酸化バナジウム）をリチウムとバナジウムとの比が１．２２：１となるように混合し、所定量のＬｉ3ＶＯ4を加えて窒素雰囲気中で１１００℃で１０時間焼成している。これにより、負極活物質はＬｉＶＯ2やＬｉ3ＶＯ4等のリチウムバナジウム酸化物を主成分とする。負極活物質に含まれるＬｉ3ＶＯ4の含有量は０．５重量％〜３．０重量％になっている。 Next, examples of the present invention will be described. A sample of the negative electrode active material of Example 1 was prepared by mixing LiOH (lithium hydroxide) and V 2 O 3 (vanadium trioxide) so that the ratio of lithium to vanadium was 1.22: 1. 3 VO 4 is added and baked at 1100 ° C. for 10 hours in a nitrogen atmosphere. Thus, the negative electrode active material is mainly composed of lithium vanadium oxide such as LiVO 2 or Li 3 VO 4 . The content of Li 3 VO 4 contained in the negative electrode active material is 0.5 wt% to 3.0 wt%.

図２は負極活物質内のＬｉ3ＶＯ4の含有量と放電容量及び負極活物質の平均粒径との関係を示している。縦軸は放電容量（単位なし）及び平均粒径（単位:μｍ）を示し、横軸はＬｉ3ＶＯ4の含有量（単位：重量％）を示している。放電容量はＬｉ3ＶＯ4の含有量が０の時（以下、この場合を比較例という）を１００とした比で表わしている。図中、Ａ１が放電容量、Ｂ１が平均粒径である。 FIG. 2 shows the relationship between the content of Li 3 VO 4 in the negative electrode active material, the discharge capacity, and the average particle size of the negative electrode active material. The vertical axis represents the discharge capacity (no unit) and the average particle size (unit: μm), and the horizontal axis represents the content of Li 3 VO 4 (unit: wt%). The discharge capacity is expressed as a ratio when the content of Li 3 VO 4 is 0 (hereinafter this case is referred to as a comparative example). In the figure, A1 is the discharge capacity and B1 is the average particle size.

Ｌｉ3ＶＯ4の含有量はＸ線回折法により測定している。平均粒径は試料をレーザー回折法により測定している。 The content of Li 3 VO 4 is measured by an X-ray diffraction method. The average particle size is measured by a laser diffraction method.

また、放電容量の試験片は負極４と同様に形成される。即ち、リチウムバナジウム酸化物から成る上記試料８０重量％、アセチレンブラック１０重量％、バインダー１０重量％を混合して銅集電体上に塗布し、１．８ｇ／ｃｍ3となるようにプレス加工して形成している。そして、金属リチウムを負極に配置して試験片を正極に配置したリチウム基準開放電位のテストセルにて０．５ｍＡ／ｃｍ2の電流密度で放電容量を測定している。 The discharge capacity test piece is formed in the same manner as the negative electrode 4. That is, 80% by weight of the above sample made of lithium vanadium oxide, 10% by weight of acetylene black, and 10% by weight of binder were mixed and applied onto a copper current collector, and pressed to 1.8 g / cm 3. Formed. The discharge capacity is measured at a current density of 0.5 mA / cm 2 in a lithium reference open potential test cell in which metallic lithium is disposed on the negative electrode and the test piece is disposed on the positive electrode.

同図によると、Ｌｉ3ＶＯ4の含有量が増加するに従い、負極活物質の平均粒径が増加していることがわかる。また、Ｌｉ3ＶＯ4の含有量が増加するに従い、放電容量も増加し、３．０重量％を超えると放電容量が減少していることがわかる。これらは、上記のようなメカニズムによるものであると考えられる。 According to the figure, it can be seen that the average particle size of the negative electrode active material increases as the content of Li 3 VO 4 increases. It can also be seen that the discharge capacity increases as the content of Li 3 VO 4 increases, and that the discharge capacity decreases when the content exceeds 3.0% by weight. These are considered to be due to the mechanism as described above.

このように、リチウムバナジウム酸化物を主成分とする負極活物質中にＬｉ3ＶＯ4を含有させ、その含有量を０．５重量％〜３．０重量％にすることで、適切な平均粒径を有する負極活物質が得られ、その負極活物質を負極に用いた非水二次電池において、Ｌｉ3ＶＯ4を負極活物質に含有していない場合と比較して、放電容量を３０〜４０％向上させることができる。このときの負極活物質の平均粒径は１０μｍ〜５０μｍである。 Thus, Li 3 VO 4 is contained in the negative electrode active material containing lithium vanadium oxide as a main component, and the content is adjusted to 0.5 wt% to 3.0 wt% to obtain an appropriate average particle size. In the non-aqueous secondary battery using the negative electrode active material for the negative electrode, the discharge capacity is 30 to 30% compared to the case where Li 3 VO 4 is not contained in the negative electrode active material. It can be improved by 40%. The average particle size of the negative electrode active material at this time is 10 μm to 50 μm.

実施例２の負極活物質の試料は、Ｌｉ3ＶＯ4を含有させずにＶＣの量を変化させてＬｉＯＨ及びＶ2Ｏ3に加えて焼成している。更に、平均粒径の影響を除くため、平均粒径が約７μｍになるようにジェットミルにより粉砕している。 The sample of the negative electrode active material of Example 2 was baked by adding VC to the amount of VC without containing Li 3 VO 4 in addition to LiOH and V 2 O 3 . Further, in order to eliminate the influence of the average particle size, the particles are pulverized by a jet mill so that the average particle size becomes about 7 μm.

図３は負極活物質内のＶＣ（バナジウム炭化物）の含有量と放電容量及び高率放電維持率との関係を示している。縦軸は放電容量及び高率放電維持率を示し、横軸はＶＣの含有量（単位：重量％）を示している。放電容量は上記比較例（ＶＣの含有量は０である）を１００とした比で表わしている。図中、Ａ２が放電容量、Ｃ２が高率放電維持率である。
上記と同様に、ＶＣの含有量は試料をＸ線回折法により測定している。尚、同図において、各試料の平均粒径（単位:μｍ）を並記している（図中、Ｂ２）。平均粒径は試料をレーザー回折法により測定している。 FIG. 3 shows the relationship between the content of VC (vanadium carbide) in the negative electrode active material, the discharge capacity, and the high rate discharge maintenance ratio. The vertical axis represents the discharge capacity and the high rate discharge maintenance ratio, and the horizontal axis represents the VC content (unit: wt%). The discharge capacity is expressed as a ratio with the comparative example (VC content is 0) as 100. In the figure, A2 is the discharge capacity, and C2 is the high rate discharge maintenance rate.
Similarly to the above, the content of VC is measured by the X-ray diffraction method of the sample. In the figure, the average particle diameter (unit: μm) of each sample is shown (B2 in the figure). The average particle size is measured by a laser diffraction method.

放電容量は上記のテストセルにて０．５ｍＡ／ｃｍ2の電流密度で測定している。高率放電維持率は上記テストセルにて０．５ｍＡ／ｃｍ2の電流密度で測定した放電容量（以下、「低率放電容量」という場合がある）を１００として、３ｍＡ／ｃｍ2の電流密度で測定した放電容量（以下、「高率放電容量」という場合がある）の比で表わしている。 The discharge capacity is measured at a current density of 0.5 mA / cm 2 in the test cell. The high rate discharge maintenance rate is 3 mA / cm 2 , where 100 is the discharge capacity measured in the test cell at a current density of 0.5 mA / cm 2 (hereinafter sometimes referred to as “low rate discharge capacity”). It is expressed by the ratio of the discharge capacity (hereinafter, sometimes referred to as “high rate discharge capacity”) measured in (1).

同図によると、ＶＣの含有量が０．５重量％以下では高い放電容量が得られるが、０．５重量％を超えると放電容量が急激に低下する。また、高率放電維持率はＶＣの含有量の増加に伴い向上する。これは、上記したように、ＶＣの体積抵抗率が低く、ＶＣの含有量が増えると粒子内の導電性が向上したためと考えられる。   According to the figure, a high discharge capacity can be obtained when the VC content is 0.5% by weight or less, but when it exceeds 0.5% by weight, the discharge capacity rapidly decreases. Further, the high rate discharge maintenance ratio is improved as the VC content is increased. This is presumably because, as described above, the volume resistivity of VC is low and the conductivity in the particles is improved when the VC content is increased.

このように、リチウムバナジウム酸化物を主成分とする負極活物質中にＶＣを含有させ、その含有量を０．５重量％にすることで、放電容量を向上させることができるだけでなく、高率放電維持率を向上させることもできる。尚、実施例１の負極活物質中にＶＣを含有させてもよい。   Thus, by containing VC in the negative electrode active material mainly composed of lithium vanadium oxide and making its content 0.5 wt%, not only can the discharge capacity be improved, but also a high rate It is also possible to improve the discharge maintenance rate. Note that VC may be contained in the negative electrode active material of Example 1.

本発明は、リチウムイオン二次電池等の非水二次電池に利用することができる。   The present invention can be used for non-aqueous secondary batteries such as lithium ion secondary batteries.

本発明の実施形態の非水二次電池を示す縦断面図The longitudinal cross-sectional view which shows the non-aqueous secondary battery of embodiment of this invention 本発明の実施形態の非水二次電池用負極材料を構成する負極活物質内のＬｉ3ＶＯ4の含有量と放電容量及び負極活物質の平均粒径との関係を示す図It shows the relationship between the average particle size of the content of Li 3 VO 4 of the negative electrode active substance in constituting the nonaqueous secondary battery negative electrode material of the embodiment and the discharge capacity and the negative electrode active material of the present invention 本発明の実施形態の非水二次電池用負極材料を構成する負極活物質内のＶＣの含有量と放電容量及び高率放電維持率との関係を示す図The figure which shows the relationship between the content of VC in the negative electrode active material which comprises the negative electrode material for nonaqueous secondary batteries of embodiment of this invention, discharge capacity, and a high rate discharge maintenance factor.

符号の説明Explanation of symbols

１ 非水二次電池
２ ケース
３ 正極
４ 負極
５ セパレータ
６ センターピン
７ 正極端子
８ 負極端子
１０ 積層体 DESCRIPTION OF SYMBOLS 1 Nonaqueous secondary battery 2 Case 3 Positive electrode 4 Negative electrode 5 Separator 6 Center pin 7 Positive electrode terminal 8 Negative electrode terminal 10 Laminated body

Claims (4)

リチウムバナジウム酸化物を主成分とした負極活物質として用いられる非水二次電池用負極材料において、前記負極活物質は０．５重量％以下のバナジウム炭化物が含まれることを特徴とする非水二次電池用負極材料。   In a negative electrode material for a non-aqueous secondary battery used as a negative electrode active material containing lithium vanadium oxide as a main component, the negative electrode active material contains 0.5% by weight or less of vanadium carbide. Negative electrode material for secondary batteries. 前記負極活物質は０．５重量％以上３．０重量％以下のＬｉ  The negative electrode active material is 0.5 wt% or more and 3.0 wt% or less of Li. 3Three ＶＯVO 4Four が更に含まれることを特徴とする、請求項１に記載の非水二次電池用負極材料。The negative electrode material for a non-aqueous secondary battery according to claim 1, further comprising: 前記負極活物質の平均粒径が１０μｍ以上５０μｍ以下であることを特徴とする、請求項２に記載の非水二次電池用負極材料。 3. The negative electrode material for a non-aqueous secondary battery according to claim 2 , wherein the negative electrode active material has an average particle size of 10 μm to 50 μm. 請求項１〜請求項３のいずれか１項に記載の非水二次電池用負極材料から成る負極活物質を有した負極と、正極と、電解質とから成ることを特徴とする非水二次電池。 A negative electrode having a negative electrode active material composed of a negative electrode material for a nonaqueous secondary battery according to any one of claims 1 to 3, a positive electrode, a non-aqueous secondary, characterized in that it consists of an electrolyte battery.
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US11/902,206 US8187750B2 (en) 2006-09-19 2007-09-19 Negative active material including lithium vanadium oxide for non-aqueous rechargeable battery, and non-aqueous rechargeable battery including same
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4404217A4 (en) * 2021-09-15 2025-07-30 Panasonic Ip Man Co Ltd COMPOSITION, BATTERY AND METHOD FOR PRODUCING THE COMPOSITION

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6233828B2 (en) * 2012-09-21 2017-11-22 国立研究開発法人産業技術総合研究所 Negative electrode for lithium ion battery, lithium ion battery comprising the negative electrode
KR101499070B1 (en) * 2012-12-27 2015-04-02 경북대학교 산학협력단 Negative composition for lithium secondary battery comprising lithium-vanadium oxide and preparation method thereof
CN104241626B (en) * 2013-06-17 2016-10-05 华南理工大学 The process for preparing sol-gel of lithium ion battery lithium vanadate negative material
CN103474641A (en) * 2013-09-25 2013-12-25 三峡大学 A kind of lithium ion battery negative electrode material Li3VO4 and preparation method thereof
CN103500821B (en) * 2013-10-18 2016-04-13 苏州德尔石墨烯产业投资基金管理有限公司 A kind of lithium ion battery electronegative potential lithium vanadium based compound and preparation method thereof
CN111933902B (en) * 2020-07-07 2021-10-08 梅州市量能新能源科技有限公司 Lithium ion battery negative electrode material, lithium ion battery and lithium ion battery preparation method
EP4538235A4 (en) 2022-06-06 2025-12-03 Panasonic Ip Man Co Ltd VANADIUM OXIDE AND BATTERY WITH IT
EP4718531A1 (en) 2023-05-22 2026-04-01 Panasonic Intellectual Property Management Co., Ltd. Vanadium oxide composite and battery using same
JPWO2024241724A1 (en) 2023-05-22 2024-11-28
EP4718533A1 (en) 2023-05-22 2026-04-01 Panasonic Intellectual Property Management Co., Ltd. Vanadium oxide composite and battery using same
WO2025121002A1 (en) 2023-12-05 2025-06-12 パナソニックＩｐマネジメント株式会社 Negative electrode active material and battery
CN121909167A (en) 2023-12-05 2026-04-21 松下知识产权经营株式会社 Lithium vanadium oxide, negative electrode active material, and battery

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029132A (en) 1976-05-24 1977-06-14 Westinghouse Electric Corporation Method of preparing high capacity nickel electrode powder
JP3169102B2 (en) * 1993-04-14 2001-05-21 セイコーインスツルメンツ株式会社 Non-aqueous electrolyte secondary battery
JPH0729604A (en) * 1993-07-14 1995-01-31 Fuji Photo Film Co Ltd Non-aqueous secondary battery
JP4352475B2 (en) * 1998-08-20 2009-10-28 ソニー株式会社 Solid electrolyte secondary battery
JP2003068305A (en) * 2001-03-01 2003-03-07 Sumitomo Metal Ind Ltd Anode material for lithium secondary battery and method for producing the same
JP3835180B2 (en) * 2001-03-05 2006-10-18 住友金属鉱山株式会社 Cathode active material for non-aqueous electrolyte secondary battery and method for producing the same
JP3876673B2 (en) * 2001-10-05 2007-02-07 住友金属鉱山株式会社 Cathode active material for non-aqueous electrolyte secondary battery
JP3950958B2 (en) * 2002-06-07 2007-08-01 独立行政法人物質・材料研究機構 Method for producing Li-V oxide
US20040048157A1 (en) 2002-09-11 2004-03-11 Neudecker Bernd J. Lithium vanadium oxide thin-film battery
JP4781659B2 (en) * 2003-11-06 2011-09-28 昭和電工株式会社 Graphite particles for negative electrode material, method for producing the same, and battery using the same
JP4400190B2 (en) * 2003-11-27 2010-01-20 株式会社豊田中央研究所 Method for producing negative electrode active material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4404217A4 (en) * 2021-09-15 2025-07-30 Panasonic Ip Man Co Ltd COMPOSITION, BATTERY AND METHOD FOR PRODUCING THE COMPOSITION

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