JP2708883B2 - Manufacturing method of non-aqueous electrolyte battery - Google Patents
Manufacturing method of non-aqueous electrolyte batteryInfo
- Publication number
- JP2708883B2 JP2708883B2 JP1151152A JP15115289A JP2708883B2 JP 2708883 B2 JP2708883 B2 JP 2708883B2 JP 1151152 A JP1151152 A JP 1151152A JP 15115289 A JP15115289 A JP 15115289A JP 2708883 B2 JP2708883 B2 JP 2708883B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- cupric oxide
- discharge
- positive electrode
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 57
- 229960004643 cupric oxide Drugs 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims 1
- 208000028659 discharge Diseases 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010949 copper Substances 0.000 description 8
- JORQDGTZGKHEEO-UHFFFAOYSA-N lithium cyanide Chemical compound [Li+].N#[C-] JORQDGTZGKHEEO-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910016609 LixCuO Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 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
Landscapes
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、リチウムもしくはリチウム合金からなる負
極と、非水電解液と、酸化第２銅を正極活物質とする正
極とからなる非水電解液電池に係るものであり、特に正
極活物質の改質に関するものである。The present invention relates to a nonaqueous electrolyte comprising a negative electrode made of lithium or a lithium alloy, a nonaqueous electrolyte, and a positive electrode containing cupric oxide as a positive electrode active material. The present invention relates to an electrolyte battery, and particularly to reforming of a positive electrode active material.
（ロ）従来の技術 リチウムまたはリチウム合金からなる負極を用いた非
水電解液電池は高エネルギー密度を有し、且つ自己放電
が少ないという利点を有する。そして、酸化第２銅（Cu
O）を正極活物質に用いれば、電池電圧が約1.5V程度と
なるので、既存のアルカリ乾電池、水銀電池、酸化銀電
池と互換使用しうる利点があり注目されている。(B) Conventional technology A non-aqueous electrolyte battery using a negative electrode made of lithium or a lithium alloy has advantages of high energy density and low self-discharge. Then, cupric oxide (Cu
If O) is used as the positive electrode active material, the battery voltage will be about 1.5 V, so that it has the advantage that it can be used interchangeably with existing alkaline dry batteries, mercury batteries, and silver oxide batteries.
ところで、この種電池は、高率放電において、放電初
期に電池電圧が落ち込む等の問題があった。By the way, this kind of battery has a problem that the battery voltage drops at the initial stage of discharge in high-rate discharge.
（ハ）発明が解決しようとする課題 本発明は、前記問題点に鑑みてなされたものであっ
て、放電初期における電池電圧の落ち込みを抑制し、放
電特性に優れた非水電解液電池を提供しようとするもの
である。(C) Problems to be Solved by the Invention The present invention has been made in view of the above problems, and provides a non-aqueous electrolyte battery that suppresses a drop in battery voltage at the initial stage of discharge and has excellent discharge characteristics. What you want to do.
（ニ）課題を解決するための手段 本発明の非水電解液電池の製造方法は、アルカリ金属
もしくはアルカリ土類金属のシアン化物もしくは水酸化
物の水溶液中に、酸化第２銅を浸漬した後、乾燥処理し
て得た正極活物質を、正極に用いることを特徴とするも
のである。(D) Means for Solving the Problems The method for producing a nonaqueous electrolyte battery according to the present invention comprises the steps of: immersing cupric oxide in an aqueous solution of a cyanide or hydroxide of an alkali metal or alkaline earth metal; The positive electrode active material obtained by the drying treatment is used for a positive electrode.
ここで、前記シアン化物もしくは前記水酸化物の水溶
液の濃度としては、0.1mol/l〜1.5mol/lであることを特
徴とするものである。Here, the concentration of the aqueous solution of the cyanide or the hydroxide is 0.1 mol / l to 1.5 mol / l.
（ホ）作用 本発明の如く、結晶性を低下させた酸化第２銅を正極
活物質として、非水電解液電池の正極に用いることによ
り、放電初期の電池電圧の落ち込みが抑制でき、平坦な
電池電圧を得ることが可能となる。(E) Function As in the present invention, by using cupric oxide having reduced crystallinity as a positive electrode active material for the positive electrode of a non-aqueous electrolyte battery, it is possible to suppress a drop in battery voltage at the initial stage of discharge, and to obtain a flat surface. It is possible to obtain a battery voltage.
従来の酸化第２銅を単に正極活物質として用いた場
合、800Ω負極で約1.25Vの電池電圧を示し、且つ放電初
期に電池電圧の落ち込みが認められる。When conventional cupric oxide is simply used as a positive electrode active material, a battery voltage of about 1.25 V is exhibited with an 800Ω negative electrode, and a drop in the battery voltage is observed at the beginning of discharging.
一方、本発明の如く、結晶性を低下させた改質酸化第
２銅を用いた場合には、約1.35Vの電池電圧を示し放電
初期の電池電圧の落ち込みが観察されない。これは結晶
性が低下していると、リチウムイオンが酸化第２銅の結
晶構造内に拡散し易いためであると推定される。On the other hand, when the modified cupric oxide having reduced crystallinity is used as in the present invention, the battery voltage is about 1.35 V, and no drop in the battery voltage at the initial stage of discharge is observed. This is presumed to be because lithium ions easily diffuse into the crystal structure of cupric oxide when the crystallinity is reduced.
更に、この機構を詳述すると、アルカリ金属もしくは
アルカリ土類金属のシアン化物もしくは水酸化物の水溶
液中に酸化第２銅を浸漬すると、銅（Cu）が少量溶出す
る。この溶出した銅に入れ代わり、アルカリ金属または
アルカリ土類金属が、酸化第２銅中に侵入したものが得
られる。これを乾燥処理すると、結晶構造にひずみを有
する即ち結晶性が低下した改質酸化第２銅が合成され
る。そしてこれが、電池の放電時においてリチウムイオ
ン（Li+）の拡散を促進するため、放電初期の電池電圧
の落ち込みが改善され、高率放電特性が向上すると考え
られる。Further, this mechanism will be described in detail. When cupric oxide is immersed in an aqueous solution of cyanide or hydroxide of an alkali metal or alkaline earth metal, a small amount of copper (Cu) is eluted. Instead of the eluted copper, an alkali metal or an alkaline earth metal invading the cupric oxide is obtained. When this is dried, modified cupric oxide having a strain in the crystal structure, that is, having reduced crystallinity, is synthesized. It is considered that this promotes the diffusion of lithium ions (Li + ) at the time of discharging the battery, so that the drop in the battery voltage at the initial stage of discharging is improved and the high-rate discharge characteristics are improved.
（ヘ）実施例 以下に本発明の実施例と比較例との対比に言及し、詳
述する。(F) Examples Hereinafter, the present invention will be described in detail with reference to comparison between examples of the present invention and comparative examples.
◎第１実験例 （実施例１） 市販特級の酸化第２銅（CuO）40gを、0.5mol/lLiCNの
希薄水溶液200ccに浸漬後、濾過して水洗し、600℃で熱
処理（乾燥処理）を行い、改質酸化第２銅（正極活物
質）を得た。ここで、前記乾燥処理時の温度は、酸化第
２銅中に水分が残存せず且つ前記酸化第２銅が分解しな
い温度とする必要があり、200〜600℃とするのが望まし
い。◎ First experimental example (Example 1) After immersing 40 g of commercially available special grade cupric oxide (CuO) in 200 cc of a 0.5 mol / l LiCN dilute aqueous solution, filtration, washing with water, and heat treatment (drying treatment) at 600 ° C. Then, a modified cupric oxide (positive electrode active material) was obtained. Here, the temperature at the time of the drying treatment needs to be a temperature at which no water remains in the cupric oxide and the cupric oxide does not decompose, and is desirably 200 to 600 ° C.
この改質酸化第２銅85重量％に、導電剤としての黒鉛
10重量％と、結着剤としてのフッ素樹脂粉末５重量％と
を加えて、混合した後、この混合物を約2ton/cm2の圧力
で加圧成型して、径15.0mm、厚み1.1mmの成形体を得
た。この成形体を200〜300℃で再度熱処理することによ
り、正極を得た。85% by weight of this modified cupric oxide was added to graphite as a conductive agent
After adding and mixing 10% by weight and 5% by weight of a fluororesin powder as a binder, the mixture was molded under pressure at a pressure of about 2 ton / cm 2 to obtain a diameter of 15.0 mm and a thickness of 1.1 mm. A molded article was obtained. This compact was heat-treated again at 200 to 300 ° C. to obtain a positive electrode.
負極は、リチウム板を約0.6mmの厚みに圧延し、この
圧延板を径15.0mmに打ち抜いたものである。The negative electrode is obtained by rolling a lithium plate to a thickness of about 0.6 mm and punching the rolled plate to a diameter of 15.0 mm.
非水電解液は、プロピレンカーボネートと１、２−ジ
メトキシエタンとの混合溶媒に、過塩素酸リチウムを1m
ol/l溶解させたものを用いた。The non-aqueous electrolytic solution is a mixed solvent of propylene carbonate and 1,2-dimethoxyethane, and 1 m of lithium perchlorate is added.
The solution dissolved in ol / l was used.
そしてセパレータとしては、ポリプロピレン不織布を
用い、外径20.0mm、厚み2.0mmの本発明電池A1を作製し
た。And as the separator, using a polypropylene nonwoven fabric, an outer diameter of 20.0 mm, the present invention battery A 1 thick 2.0mm was prepared.
（実施例２） 前記実施例１において、LiCN水溶液の代わりにNaCN水
溶液を用いた以外は同様にして、正極活物質を得、本発
明電池A2を作製した。(Example 2) Example 1, except for using NaCN aqueous solution instead of LiCN solution in the same manner, to obtain a cathode active material was prepared present battery A 2.
（実施例３） 前記実施例１において、LiCN水溶液の代わりにLiOH水
溶液を用いた以外は同様にして、正極活物質を得、本発
明電池A3を作製した。(Example 3) Example 1 except for using aqueous LiOH instead of LiCN solution in the same manner, to obtain a cathode active material was prepared present battery A 3.
（比較例１） 前記実施例１において用いた改質酸化第２銅に代え
て、市販特級の酸化第２銅を正極活物質として用いた以
外は同様にして、比較電池Ｂを作製した。(Comparative Example 1) A comparative battery B was produced in the same manner except that a commercially available special grade of cupric oxide was used as the positive electrode active material instead of the modified cupric oxide used in Example 1 above.
（比較例２） 前記実施例１において用いた改質酸化第２銅に代え
て、硫酸銅水溶液と水酸化リチウム水溶液から作製した
リチウム含有水酸化銅を熱分解することにより得た、リ
チウム含有酸化第２銅を正極活物質として用いた以外は
同様にして、比較電池Ｃを作製した。Comparative Example 2 A lithium-containing oxide obtained by thermally decomposing a lithium-containing copper hydroxide prepared from an aqueous copper sulfate solution and an aqueous lithium hydroxide solution in place of the modified cupric oxide used in Example 1 above. Comparative Battery C was prepared in the same manner except that cupric copper was used as the positive electrode active material.
これら各電池に用いた、各酸化第２銅の結晶構造につ
いて検討した。ここでは、各酸化第２銅のＸ線回析（Cu
Kα線）におけるメインピーク（２θ＝35.5°）の半値
幅を求め、比較するというものである。The crystal structure of each cupric oxide used in each of these batteries was examined. Here, the X-ray diffraction (Cu
The half width of the main peak (2θ = 35.5 °) at the Kα line is determined and compared.
この結果を、第１表に示す。 The results are shown in Table 1.
第１表より、本発明電池の正極活物質として用いた改
質酸化第２銅は、市販特級の酸化第２銅（比較電池Ｂ）
に比べて、その半値幅が約20％大きくなっており、結晶
構造にひずみが生じている即ち結晶性が低下していると
考えられる。比較電池Ｃの正極活物質は、市販特級の酸
化第２銅と、同等の半値幅でありその結晶構造にひずみ
を生じていないと考えられる。 According to Table 1, the modified cupric oxide used as the positive electrode active material of the battery of the present invention is a commercially available special grade cupric oxide (comparative battery B).
It is considered that the half value width is about 20% larger than that of, and the crystal structure is distorted, that is, the crystallinity is lowered. It is considered that the positive electrode active material of Comparative Battery C has a half-value width equivalent to that of commercially available special-grade cupric oxide and has no distortion in its crystal structure.
次に、これら本発明電池A1，A2，A3及び比較電池B,C
を用い、電池の放電特性を比較した。この時の放電条件
は、温度25℃、負荷800Ωで放電するというものであ
る。この放電負荷800Ωという値は、この種の電池にお
いて、高率放電に相当する。Next, these batteries A 1 , A 2 , A 3 of the present invention and comparative batteries B, C
Was used to compare the discharge characteristics of the batteries. The discharge conditions at this time are discharge at a temperature of 25 ° C. and a load of 800Ω. This value of 800 Ω discharge load corresponds to a high rate discharge in this type of battery.
この結果を、第１図に示す。これより、本発明電池
A1，A2，A3は、比較電池B,Cに比べて、放電容量が大き
いことがわかる。また、本発明電池A1，A2，A3は、放電
初期の電池電圧の落ち込みがほとんど観察されないこと
が理解される。The result is shown in FIG. Thus, the battery of the present invention
It can be seen that A 1 , A 2 , and A 3 have larger discharge capacities than the comparative batteries B and C. It is also understood that the batteries A 1 , A 2 and A 3 of the present invention show almost no drop in the battery voltage at the initial stage of discharging.
◎第２実験例 更に、酸化第２銅を浸漬するアルカリ金属塩もしくは
アルカリ土類金属塩の水溶液の種類を変化させて、改質
酸化第２銅を得、これを正極活物質として用いることに
より、種々の本発明電池を得た。この電池の作製は、前
記実施例１に準じた。そして、これら電池を前記同様の
放電条件にて、放電させて、放電初期の電池電圧の落ち
込みが観察される辺りの電池電圧を測定し、放電初期の
電池電圧を調べた。◎ Second Experimental Example Further, by changing the type of the aqueous solution of the alkali metal salt or alkaline earth metal salt in which the cupric oxide is immersed, a modified cupric oxide is obtained, and this is used as the positive electrode active material. Thus, various batteries of the present invention were obtained. The fabrication of this battery was in accordance with Example 1. Then, these batteries were discharged under the same discharge conditions as described above, and the battery voltage around the point where a drop in the battery voltage at the initial stage of the discharge was observed was measured, and the battery voltage at the initial stage of the discharge was examined.
この結果を、第２表に示す。 The results are shown in Table 2.
これより、本発明電池は、放電初期の電圧の落ち込み
がほとんど観察されないことがわかる。 This shows that in the battery of the present invention, a drop in voltage at the initial stage of discharge is hardly observed.
この理由を考察すると、本発明電池において、アルカ
リ金属もしくはアルカリ土類金属のシアン化物もしくは
水酸化物の水溶液中に酸化第２銅を浸漬することによ
り、酸化第２銅が溶解し、銅が溶出することが観察され
る。この時溶出した銅に入れ代わり、アルカリ金属もし
くはアルカリ土類金属が、酸化第２銅中に侵入する。こ
れを乾燥処理することにより、結晶構造にひずみを有す
る即ち結晶性の低い改質酸化第２銅が得られる。そし
て、これを正極活物質として用いることにより、リチウ
ムイオンの拡散し難い放電初期においても、前記結晶構
造内へのリチウムイオンの拡散がし易くなり、放電電圧
の落ち込みが解消される。更に、この改質酸化第２銅
は、リチウムイオンが拡散し易いものであるため、放電
容量も大きくなり、高率放電特性も向上すると考えられ
る。Considering the reason, in the battery of the present invention, by immersing cupric oxide in an aqueous solution of a cyanide or hydroxide of an alkali metal or an alkaline earth metal, the cupric oxide dissolves and copper is eluted. It is observed that At this time, the alkali metal or alkaline earth metal enters the cupric oxide instead of the copper eluted. By subjecting this to a drying treatment, modified cupric oxide having a strain in the crystal structure, that is, low crystallinity, can be obtained. By using this as a positive electrode active material, even at the beginning of discharge in which lithium ions are not easily diffused, lithium ions are easily diffused into the crystal structure, and a drop in discharge voltage is eliminated. Further, since the modified cupric oxide easily diffuses lithium ions, it is considered that the discharge capacity is increased and the high-rate discharge characteristics are also improved.
尚、比較電池Ｃにおいても放電初期の電圧の落ち込み
がほとんど認められなかったが、これは正極活物質中の
リチウムを含む酸化第２銅（LixCuO）が触媒的に作用
し、放電初期においてリチウムイオンをとり込み易くし
ていることに起因すると考えられる。In the comparative battery C, almost no drop in the voltage at the initial stage of the discharge was observed. This is because the cupric oxide (LixCuO) containing lithium in the positive electrode active material acted as a catalyst and the lithium ion was discharged at the initial stage of the discharge. This is considered to be due to the fact that it is easy to incorporate
◎第３実験例 ここでは、酸化第２銅を浸漬するアルカリ金属塩もし
くはアルカリ土類金属塩の水溶液の濃度を変化させて、
電池特性の比較、検討を行った。具体的には、使用せる
水溶液をLiCN水溶液とし、これを用いて前記実施例１と
同様にして電池を得、温度20℃、負荷800Ωで電池を放
電させるというものである。尚、浸漬時間は12時間と
し、浸漬温度は室温であった。そして、この時間のLiCN
水溶液の濃度と、各電池の放電容量とを比較した。◎ Third Experimental Example Here, the concentration of the aqueous solution of the alkali metal salt or alkaline earth metal salt in which the cupric oxide was immersed was changed,
The battery characteristics were compared and examined. Specifically, an aqueous solution to be used is a LiCN aqueous solution, and a battery is obtained in the same manner as in Example 1 using the LiCN aqueous solution, and the battery is discharged at a temperature of 20 ° C. and a load of 800Ω. The immersion time was 12 hours, and the immersion temperature was room temperature. And this time LiCN
The concentration of the aqueous solution was compared with the discharge capacity of each battery.
この結果を、第２図に示す。これより、濃度0.1mol/l
〜1.5mol/lの範囲において、LiCN水溶液への浸漬効果が
顕著であり、電池の放電容量が増加していることがわか
る。ここで、濃度が1.5mol/lを越えると電池の放電容量
が低下するのは、浸漬時に溶出する銅の量が過多になる
ためであると考えられる。The result is shown in FIG. From this, the concentration is 0.1 mol / l
It can be seen that the immersion effect in the aqueous solution of LiCN is remarkable in the range of 1.51.5 mol / l, and the discharge capacity of the battery is increased. Here, it is considered that the reason why the discharge capacity of the battery decreases when the concentration exceeds 1.5 mol / l is that the amount of copper eluted during immersion becomes excessive.
この水溶液の濃度が0.1mol/l〜1.5mol/lの範囲が特に
好ましいという傾向は、他のアルカリ金属塩及びアルカ
リ土類金属塩を用いた場合においても、同様に観察され
た。The tendency that the concentration of the aqueous solution is particularly preferably in the range of 0.1 mol / l to 1.5 mol / l was similarly observed when other alkali metal salts and alkaline earth metal salts were used.
（ト）発明の効果 本発明の非水電解液電池によれば、改質された酸化第
２銅を正極活物質として用いているので、放電初期の電
池電圧の落ち込みを抑制することができ、電池の放電容
量を大きくし、高率放電特性を向上しうるものであり、
その工業的価値は極めて大きい。(G) Effect of the Invention According to the nonaqueous electrolyte battery of the present invention, since the modified cupric oxide is used as the positive electrode active material, it is possible to suppress a drop in the battery voltage at the initial stage of discharge, It can increase the discharge capacity of the battery and improve the high rate discharge characteristics,
Its industrial value is extremely large.
第１図は電池の放電特性図、第２図はLiCN水溶液濃度と
電池の放電容量との関係を示す図である。 A1，A2，A3…本発明電池、B,C…比較電池。FIG. 1 is a diagram showing the discharge characteristics of the battery, and FIG. 2 is a diagram showing the relationship between the LiCN aqueous solution concentration and the discharge capacity of the battery. A 1 , A 2 , A 3 ... batteries of the present invention, B, C ... comparative batteries.
Claims (2)
シアン化物もしくは水酸化物の水溶液中に、酸化第２銅
を浸漬した後、乾燥処理して得た正極活物質を、正極に
用いることを特徴とする非水電解液電池の製造方法。1. A positive electrode active material obtained by immersing cupric oxide in an aqueous solution of a cyanide or hydroxide of an alkali metal or alkaline earth metal, followed by drying treatment, is used for the positive electrode. A method for producing a nonaqueous electrolyte battery.
溶液の濃度が、0.1mol/1〜1.5mol/1であることを特徴と
する請求項（１）記載の非水電解液電池の製造方法。2. The method according to claim 1, wherein the concentration of the aqueous solution of the cyanide or the hydroxide is 0.1 mol / 1 to 1.5 mol / 1. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1151152A JP2708883B2 (en) | 1989-06-14 | 1989-06-14 | Manufacturing method of non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1151152A JP2708883B2 (en) | 1989-06-14 | 1989-06-14 | Manufacturing method of non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0317960A JPH0317960A (en) | 1991-01-25 |
| JP2708883B2 true JP2708883B2 (en) | 1998-02-04 |
Family
ID=15512496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1151152A Expired - Fee Related JP2708883B2 (en) | 1989-06-14 | 1989-06-14 | Manufacturing method of non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2708883B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0675399B2 (en) * | 1986-01-20 | 1994-09-21 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
-
1989
- 1989-06-14 JP JP1151152A patent/JP2708883B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0317960A (en) | 1991-01-25 |
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