JPS6040670B2 - Manufacturing method for positive electrode active material for solid electrolyte batteries - Google Patents
Manufacturing method for positive electrode active material for solid electrolyte batteriesInfo
- Publication number
- JPS6040670B2 JPS6040670B2 JP52069305A JP6930577A JPS6040670B2 JP S6040670 B2 JPS6040670 B2 JP S6040670B2 JP 52069305 A JP52069305 A JP 52069305A JP 6930577 A JP6930577 A JP 6930577A JP S6040670 B2 JPS6040670 B2 JP S6040670B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- electrode active
- solid electrolyte
- battery
- 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
Links
- 239000007774 positive electrode material Substances 0.000 title claims description 26
- 239000007784 solid electrolyte Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 9
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical group [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- IZBLACFKNGWOAY-UHFFFAOYSA-N CCCCN1C=CC=CC1.I Chemical compound CCCCN1C=CC=CC1.I IZBLACFKNGWOAY-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- -1 lithium halides Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical group [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y02E60/12—
Landscapes
- Conductive Materials (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
本発明は固体電解質電池の正極活物質の製造法に関する
もので、化学的に安定で、エネルギー密度が高く、かつ
電池放電時の分極の小さい正極活物質を提供することを
目的とする。[Detailed Description of the Invention] The present invention relates to a method for producing a positive electrode active material for a solid electrolyte battery, and it is an object of the present invention to provide a positive electrode active material that is chemically stable, has high energy density, and has low polarization during battery discharge. With the goal.
リチウムを負極活性物質とする固体電解質電池は、銀あ
るいは銅を負極とする固体電解質電池に比べ、高イオン
導電性リチウム固体電解質が得られていないため、供給
可能な電流値（以下出力電流値という）は数ムＡ〜数１
０仏Ａである。Solid electrolyte batteries that use lithium as the negative electrode active material do not have a high ionic conductivity lithium solid electrolyte compared to solid electrolyte batteries that use silver or copper as the negative electrode, so the current value that can be supplied (hereinafter referred to as output current value) is ) is number A to number 1
0 Buddha A.
しかし近年、例えば液晶表示電子ウオッチで約５仏Ａ程
度というように電子機器の低消費電流化が進みト低出力
電流であっても高エネルギー密度の電流が要求されるに
および、リチウムを負極とする団体電解質電池は、起電
力が銀あるいは銅を負極とする固体電解質電池の０．５
〜２．０Ｖに比べ、１．５〜３．５Ｖと高く、高エネル
ギー密度化が可能なため、注目され始めている。リチウ
ム固体電解質電池の特徴である高エネルギー密度化をさ
らに改善することを目指して、電池のもう一方の極であ
る正極の宿物質として下表に示したものが主に今までに
提案されている。However, in recent years, the current consumption of electronic devices has become lower, for example, about 5 French A for liquid crystal display electronic watches, and high energy density current is required even with low output current. The electromotive force of a group electrolyte battery is 0.5 that of a solid electrolyte battery with a silver or copper negative electrode.
It is starting to attract attention because it has a high energy density of 1.5 to 3.5V compared to ~2.0V and can achieve high energy density. Aiming to further improve the high energy density that is a feature of lithium solid electrolyte batteries, the materials shown in the table below have been mainly proposed so far as host materials for the positive electrode, which is the other electrode of the battery. .
これらのなかで、ハロゲン、ポリハロゲン化物は、起電
力が高く、高エネルギー密度を得ることが可能であるが
、高腐食性であり正極集電体としてチタン、ジルコニウ
ムのごとき高価で、かつ加工性の悪い材料を必要とする
とともに、化学的に不安定で常温において高騰食性のハ
ロゲン蒸気を発生することから電池用途としては経済性
および安全性の面から好ましくない。金属酸化物も、起
電力が高く、高エネルギー密度を得ることが可能である
が、電池放電生成物が不良導体の酸化リチウムであるた
め、放電進行に伴う分極が大きく好ましくない。Among these, halogens and polyhalides have a high electromotive force and can provide high energy density, but they are highly corrosive and are expensive and difficult to process as positive electrode current collectors such as titanium and zirconium. In addition to requiring materials with poor quality, it is chemically unstable and generates corrosive halogen vapor at room temperature, making it undesirable for battery applications from the economical and safety standpoints. Metal oxides also have a high electromotive force and can provide a high energy density, but since the battery discharge product is lithium oxide, which is a poor conductor, it is not preferable because it causes large polarization as the discharge progresses.
金属ハロゲン化物と金属硫化物は化学的に安定であると
ともに正極集電材料も母金属あるいは母金属よりもイオ
ン化傾向の小さい金属の使用が可能で、その選択は経済
性、加工性を加味して十分検討できる余地を有している
上、電池放電生成物は、イオン伝導性のハロゲン化リチ
ウム、硫化リチウムであり放電進行に伴う分極が４・さ
し、利点を有しているが、起電力が１．５〜２．０Ｖと
低く、リチウム電池の特徴である高エネルギー密度を十
分発揮することができない。以上のように、今まで提案
されているリチウム固体電解質電池の正極活物質として
、安全性、放電性能、および高エネルギー密度を満足す
るものはない。Metal halides and metal sulfides are chemically stable, and it is possible to use a parent metal or a metal with a smaller ionization tendency than the parent metal as the positive electrode current collector material, and the selection should be made taking into account economic efficiency and processability. In addition, the battery discharge products are ion-conductive lithium halides and lithium sulfides, which have the advantage of polarization as the discharge progresses, but the electromotive force is as low as 1.5 to 2.0V, making it impossible to fully exhibit the high energy density that characterizes lithium batteries. As described above, none of the cathode active materials for lithium solid electrolyte batteries that have been proposed so far satisfy safety, discharge performance, and high energy density.
本発明は、以上に鑑み、安全性、放電性能及び高エネル
ギー密度を満足する固体電解質電池を与える正極活物質
を提供することを目的とする。In view of the above, an object of the present invention is to provide a positive electrode active material that provides a solid electrolyte battery that satisfies safety, discharge performance, and high energy density.
本発明は、無水沃化リチウムと沃化１−アルキルピリジ
ンとの溶融反応物からなるリチウムィオンン導電性固体
電解質を用いる電池の正極活物質の製造法で、前記固体
電解質と硫化鋼の混合物を１１０〜２００ｏｏの温度域
で加熱処理することにより、硫化鋼の表面に前記固体電
解質が融解して固化した被覆層を形成することを特徴と
する。本発明の方法により、硫化銅粒子を被覆するりチ
ウムィオン導電性固体電解質が硫化鋼粒子間のりチウム
ィオンの流れを円滑にし、分極の小さい正極活物質を与
える。The present invention is a method for producing a positive electrode active material for a battery using a lithium ion conductive solid electrolyte made of a molten reaction product of anhydrous lithium iodide and 1-alkylpyridine iodide. It is characterized in that a coating layer in which the solid electrolyte is melted and solidified is formed on the surface of the sulfurized steel by heat treatment in a temperature range of 110 to 200 oo. According to the method of the present invention, the lithium ion conductive solid electrolyte covering the copper sulfide particles facilitates the flow of lithium ions between the sulfide steel particles, providing a positive electrode active material with low polarization.
ここに用いる固体電解質のイオン導電性は、例えば無水
沃化リチウムと沃化１−ブチルピリジンとの溶融反応物
の場合常温で１０‐４Ｑ‐１仇‐１程度である。以下本
発明をその実施例により説明する。The ionic conductivity of the solid electrolyte used here is, for example, about 10-4Q-1-1 at room temperature in the case of a molten reaction product of anhydrous lithium iodide and 1-butylpyridine iodide. The present invention will be explained below with reference to Examples.
第１図は、本発明の正極活物質の効果を判定するために
用いたりチウム固体電解質電池の断面図である。FIG. 1 is a cross-sectional view of a lithium solid electrolyte battery used for determining the effectiveness of the positive electrode active material of the present invention.
１は厚み０．３側、直径１０．５側のステンレス鋼円板
よりなる負極集電体、２は厚み０．４肌、直径１０．５
胸のＩＪチウム負極、３は沃化リチウム含量が８７．５
モル分率の沃化リチウムと沃化１ーブチルピリジン溶融
化合物より成る厚さ０．５柵のりチウムィオン導電性固
体電質層、４は正極合剤保持用の樹脂リング、５は３ト
ンノ地の圧力で１．５肋の厚みに成型された正極合剤で
ある。1 is a negative electrode current collector made of a stainless steel disk with a thickness of 0.3 and a diameter of 10.5, and 2 is a negative electrode current collector with a thickness of 0.4 and a diameter of 10.5.
Chest IJ lithium negative electrode, 3 has lithium iodide content of 87.5
A lithium ion conductive solid electrolyte layer with a thickness of 0.5 mm consisting of a mole fraction of lithium iodide and 1-butylpyridine iodide, 4 is a resin ring for holding the positive electrode mixture, 5 is a 3 tonne ground pressure. This is a positive electrode mixture molded to a thickness of 1.5 ribs.
６は厚み０．３職の銅円板よりなる正極集電体である。6 is a positive electrode current collector made of a copper disk with a thickness of 0.3 mm.
特に、銅円板を選んだのは電池保存中、正極合剤と正極
集電体の反応による性能劣下が起こらない理由による。
７は樹脂製の電池容器、８，９は各々負極、正極端子用
の飾りード線である。電池の組み立ては、負極集電板１
、負極２、電解質層３、樹脂リング４、正極合剤５、正
極集電体６を配置し、次に、上下から５トン／仇の圧力
で加圧成型した後、銀ペーストにより銅リード線８，９
を負、正極集電極に接着し、最後に電池全体をェポキシ
樹脂等の絶縁性樹脂被膜で包み込むことにより行われる
。In particular, a copper disk was chosen because it would not cause performance deterioration due to reaction between the positive electrode mixture and the positive electrode current collector during battery storage.
Reference numeral 7 designates a resin battery container, and reference numerals 8 and 9 designate decorative wires for the negative and positive terminals, respectively. To assemble the battery, the negative electrode current collector plate 1
, the negative electrode 2, the electrolyte layer 3, the resin ring 4, the positive electrode mixture 5, and the positive electrode current collector 6 are placed, and then pressure molded from above and below at a pressure of 5 tons/h, and then copper lead wires are formed using silver paste. 8,9
This is done by adhering the battery to the negative and positive collector electrodes, and finally wrapping the entire battery in an insulating resin film such as epoxy resin.
本発明に従う正極活物質は次のようにして製造される。The positive electrode active material according to the present invention is manufactured as follows.
Ｌｊｌ・９日２０を大気中２００ｑｏで２４時間加熱す
ることにより得られた無水沃化リチウムと、沃化１−ブ
チルピリジンを好適例とする沃化１ーアルキルピリジン
とを、無水沃化リチウムが９７．５〜７０モル分率、最
適には８０モル分率であるように混合し、この混合物を
大気中１５０Ｃ○で２岬時間以上加熱溶融後、溶融物を
除湿したふん囲気で、チタン坂上に流して固化する。固
形物を２００メッシュ通過１００％の粉体に粉砕し、沃
化リチウムと沃化１ーアルキルピリジンの溶融反応物と
する。次に、この溶融反応物１重量部（以下単に部とい
う）に対して硫化第２銅を好適例とする硫化鋼２〜４部
（最適には３部）を加えた混合物を大気中１１０℃〜２
００ｏｏの温度域で加熱処理後、２００メッシュ通過１
００％の粉体に粉砕し正極宿物質とする。このようにし
て得られた正極活物質は、リチウム電池の起電力として
、硫化第２銅とＩＪチウムの組み合わせで得られる理論
電圧２．０７ボルトより０．総ボルト高い２．７５ボル
トを与えるのが特徴である。硫化第１銅では起電力２．
７０ボルトを与える。第２図に、本発明に従う正極活物
質を有し第１図で示される構造の電池Ａと、従釆から提
案されている正極活物質のうち最も良好であると考えら
れている金属ハロゲン化物と金属硫化物のうち、硫化鉛
４の重量分率、沃化鉛４の重量分率、鉛粉２の重量分率
よりなる正極猪物質とし第１図で示される構造の電池Ｂ
と、１１０午０〜２００ｑ○の加熱処理を行わない硫化
第２銅３部と、沃化リチウムと沃化１−ブチルピリジン
の溶融反応物１部の混合物を正極活物質とした第１図に
示す構造の電池Ｃについて、２０ｑｏで１０仏Ａ定電流
放電時の端子電圧の経時変化を示す。起電力は電池Ａが
２．７５ボルト、電池Ｂが１．８５ボルト、電池Ｃが２
．０５ボルトである。第２図から明らかなように本発明
に従う正極徒物質を用いた電池Ａは、従来の電池Ｂより
分極が小さく、起電力が０．９Ｖ高いだけ、より高いエ
ネルギー密度化が達成されている。なお、硫化第１銅と
硫化第２銅は起電力が硫化第２鋼が０．０取高い他、同
一の挙動を示す。また、このような効果は、単に硫化鋼
を正極活性物質に用いることのみにより達成でき難いこ
とは、第２図の電池Ａと蟹池Ｃの放電曲線を比較すれば
明らかである。すなわち、本発明に従う正極活物質の加
熱処理温度を１１０ｏｏ〜２００ｏｏとしたのは、起電
力２．７５Ｖを示す正極宿物質は、理由はよくわからな
いが、沃化リチウムと沃化１−アルキルピリジンの溶融
反応物と硫化銅の混合物のうち、加熱により該溶融反応
物が混合物中で融解固化した混合物に限られ、また溶融
物の融点のうち、沃化リチウムの含量９７．５モル分率
でアルキル基がメチル基である溶融反応物の融点が最も
高く１１０こ０であることにより、加熱処理温度の下限
が１１０ｑｏとされる。上限は、硫化銅の分解温度２０
０℃で規定される。加熱処理時間は、溶融反応物が完全
に融解するまでの時間であり、特に規定はされない。な
お、沃化１−アルキルピリジンのアルキル基としては、
メチル基、エチル基、プロピル基、プチル基が用いられ
る。Anhydrous lithium iodide obtained by heating Ljl. The mixture is mixed at a mole fraction of 97.5 to 70, optimally 80 mole fraction, and heated and melted at 150C in the atmosphere for more than 2 hours. to solidify. The solid material is pulverized into a 100% powder that passes through 200 mesh to obtain a molten reaction product of lithium iodide and 1-alkylpyridine iodide. Next, a mixture of 2 to 4 parts (optimally 3 parts) of sulfurized steel, preferably cupric sulfide, was added to 1 part by weight (hereinafter simply referred to as "part") of this molten reactant at 110°C in the atmosphere. ~2
Passed through 200 mesh after heat treatment in the temperature range of 00oo 1
It is ground into 0.00% powder and used as a positive electrode host material. The positive electrode active material thus obtained has an electromotive force of 0.0 volts for a lithium battery, which is higher than the theoretical voltage of 2.07 volts obtained by the combination of cupric sulfide and IJ thium. It is characterized by providing a high total voltage of 2.75 volts. For cuprous sulfide, the electromotive force is 2.
Gives 70 volts. FIG. 2 shows a battery A having the structure shown in FIG. 1 and having a positive electrode active material according to the present invention, and a metal halide which is considered to be the best among the positive electrode active materials proposed by the related art. Battery B has the structure shown in FIG. 1 with a positive electrode material consisting of a weight fraction of lead sulfide 4, a weight fraction of lead iodide 4, and a weight fraction of lead powder 2 among metal sulfides.
In Fig. 1, a mixture of 3 parts of cupric sulfide without heat treatment of 110 pm to 200 q○ and 1 part of a molten reaction product of lithium iodide and 1-butylpyridine iodide was used as a positive electrode active material. For battery C having the structure shown, the change in terminal voltage over time during constant current discharge of 10 A at 20 qo is shown. The electromotive force is 2.75 volts for battery A, 1.85 volts for battery B, and 2 for battery C.
．． 05 volts. As is clear from FIG. 2, the battery A using the positive electrode material according to the present invention has smaller polarization than the conventional battery B, has a higher electromotive force by 0.9 V, and achieves higher energy density. Note that cuprous sulfide and cupric sulfide exhibit the same behavior except that the electromotive force of cupric sulfide steel is 0.0 higher. Furthermore, it is clear from a comparison of the discharge curves of batteries A and crab pond C in FIG. 2 that it is difficult to achieve such an effect simply by using sulfide steel as the positive electrode active material. That is, the reason why the heat treatment temperature of the positive electrode active material according to the present invention was set to 110 oo to 200 oo is because the positive electrode host material exhibiting an electromotive force of 2.75 V is composed of lithium iodide and 1-alkyl pyridine iodide, although the reason is not clear. Among the mixtures of molten reactants and copper sulfide, the molten reactants are limited to those in which the molten reactants are melted and solidified in the mixture by heating. Since the melting point of the molten reactant whose group is a methyl group is the highest, 110 qo, the lower limit of the heat treatment temperature is set to 110 qo. The upper limit is the decomposition temperature of copper sulfide 20
Defined at 0°C. The heat treatment time is the time until the molten reactant is completely melted, and is not particularly specified. In addition, as the alkyl group of 1-alkylpyridine iodide,
Methyl, ethyl, propyl, and butyl groups are used.
第３図は、本発明に従う正極活物質原料の組成のうち、
硫化鋼の合量を、沃化リチウムと沃化１−ブチルピリジ
ン溶融反応物１部に対して０〜８部の範囲で変化させた
正極宿物質を用いたりチウム電池の起電力、内部抵抗を
示し、第４図は同電池の２０ｏｏにおける５腿Ｑ定抵抗
負荷の放電曲線を示している。FIG. 3 shows the composition of the positive electrode active material raw material according to the present invention.
The electromotive force and internal resistance of a lithium battery can be improved by using a cathode host material in which the total amount of sulfide steel is varied in the range of 0 to 8 parts per part of the molten reactant of lithium iodide and 1-butylpyridine iodide. FIG. 4 shows the discharge curve of the same battery under a 5-thigh Q constant resistance load at 20 oo.
硫化鋼の含量が２部〜４部の範囲において内部抵抗が低
く、かつ電池放電時の内部抵抗増大による閉路電圧低下
の４・さし、電池を提供することができる。硫化銅につ
いて、硫化第１銅と硫化第２銅は、起電力差が０．０５
ボルトである以外、他の特性は全く同じである。以上の
ように、本発明に従う正極活物質を用いることにより安
全性、放電性能に優れた高エネルギー密度リチウム固体
電解質電池を提供することができる。When the content of sulfurized steel is in the range of 2 parts to 4 parts, it is possible to provide a battery that has a low internal resistance and a decrease in closed circuit voltage of 4 mm due to an increase in internal resistance during battery discharge. Regarding copper sulfide, the difference in electromotive force between cuprous sulfide and cupric sulfide is 0.05.
Other than being a bolt, all other characteristics are exactly the same. As described above, by using the positive electrode active material according to the present invention, a high energy density lithium solid electrolyte battery with excellent safety and discharge performance can be provided.
第１図はリチウム固体電解質電池の断面図である。
第２図は本発明に従う正極活性物質を用いたりチウム固
体電解質電池Ａと従来の正極活物質を用いたりチウム固
体電解質電池Ｂ，Ｃの定電流１０〆Ａ放電曲線を示す。
第３図は本発明に従う正極活物質原料の組成のうち、硫
化鋼含量を変化させた際の電池の内部抵抗および起電力
変化を示し、第４図はこの際の５紺○定抵抗負荷による
放電曲線を示す。第１図
第２図
第３図
第４図FIG. 1 is a cross-sectional view of a lithium solid electrolyte battery. FIG. 2 shows the constant current 10A discharge curves of lithium solid electrolyte battery A using the positive electrode active material according to the present invention and lithium solid electrolyte batteries B and C using the conventional positive electrode active material.
Figure 3 shows the changes in internal resistance and electromotive force of the battery when the sulfide steel content is changed in the composition of the positive electrode active material raw material according to the present invention, and Figure 4 shows the changes in the internal resistance and electromotive force of the battery when the sulfide steel content is changed. The discharge curve is shown. Figure 1 Figure 2 Figure 3 Figure 4
Claims (1)
溶融反応物からなるリチウムイオン導電性固体電解質を
用いる電池の正極活物質の製造法であつて、前記固体電
解質と硫化銅の混合物を、１１０〜２００℃の温度域で
加熱処理して、硫化銅の表面に前記電解質の固化した被
覆層を形成することを特徴とする固体電解質電池の正極
活物質製造法。 ２ 前記混合物の組成が、前記固体電解質１重量部に対
し、硫化銅２〜４重量部である特許請求の範囲第１項記
載の固体電解質電池の正極活物質製造法。 ３ 沃化１−アルキルピリジンのアルキル基が、ｎ−ブ
チル基である特許請求の範囲第１項又は第２項記載の団
体電解質電池の正極活物質製造法。 ４ 硫化銅が、硫化第２銅である特許請求の範囲第１〜
３項のいずれかに記載の固体電解質電池の正極活物質製
造法。[Scope of Claims] 1. A method for producing a positive electrode active material for a battery using a lithium ion conductive solid electrolyte consisting of a molten reaction product of anhydrous lithium iodide and 1-alkylpyridine iodide, comprising: A method for producing a positive electrode active material for a solid electrolyte battery, comprising heating a copper mixture at a temperature range of 110 to 200°C to form a solidified coating layer of the electrolyte on the surface of copper sulfide. 2. The method for producing a positive electrode active material for a solid electrolyte battery according to claim 1, wherein the composition of the mixture is 2 to 4 parts by weight of copper sulfide per 1 part by weight of the solid electrolyte. 3. The method for producing a positive electrode active material for a collective electrolyte battery according to claim 1 or 2, wherein the alkyl group of the 1-alkylpyridine iodide is an n-butyl group. 4 Claims 1 to 4, wherein the copper sulfide is cupric sulfide.
A method for producing a positive electrode active material for a solid electrolyte battery according to any one of Item 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52069305A JPS6040670B2 (en) | 1977-06-10 | 1977-06-10 | Manufacturing method for positive electrode active material for solid electrolyte batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52069305A JPS6040670B2 (en) | 1977-06-10 | 1977-06-10 | Manufacturing method for positive electrode active material for solid electrolyte batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS544323A JPS544323A (en) | 1979-01-13 |
| JPS6040670B2 true JPS6040670B2 (en) | 1985-09-12 |
Family
ID=13398705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52069305A Expired JPS6040670B2 (en) | 1977-06-10 | 1977-06-10 | Manufacturing method for positive electrode active material for solid electrolyte batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6040670B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5882468A (en) * | 1981-11-11 | 1983-05-18 | Nec Corp | Positive pole substance for battey and manufacture thereof |
| JPS5885269A (en) * | 1981-11-13 | 1983-05-21 | Nec Corp | Battery positive electrode body and its manufacturing method |
| JPS5885270A (en) * | 1981-11-16 | 1983-05-21 | Nec Corp | Positive electrode for battery and its manufacture |
| JPS5887758A (en) * | 1981-11-17 | 1983-05-25 | Nec Corp | Battery positive electrode body and its manufacturing method |
-
1977
- 1977-06-10 JP JP52069305A patent/JPS6040670B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS544323A (en) | 1979-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1165815A (en) | Electrochemical cell and method of manufacture | |
| CN101154725B (en) | Negative electrode active material for nonaqueous rechargeable battery and nonaqueous rechargeable battery thereof | |
| JPS623547B2 (en) | ||
| JPS6040670B2 (en) | Manufacturing method for positive electrode active material for solid electrolyte batteries | |
| JP2643344B2 (en) | Lithium-based thermal battery | |
| JPS5960814A (en) | Lithium oxide amorphous ionic conductor | |
| WO2025113341A1 (en) | Gallium-based alloy, preparation method therefor and use thereof | |
| JPS5952515B2 (en) | Manufacturing method for positive electrode active material for solid electrolyte batteries | |
| JPH06275314A (en) | Lithium secondary battery | |
| JP2007227072A (en) | Electrochemical cell | |
| JPH05325961A (en) | Lithium battery | |
| JPH01128354A (en) | Nonaqueous solvent cell | |
| JPS5849965B2 (en) | Manufacturing method of lithium ion conductive solid electrolyte | |
| JPS60198067A (en) | solid electrolyte secondary battery | |
| JPS5820106B2 (en) | Yuuki Denkai Shitsudenchi | |
| JPS6012677A (en) | solid electrolyte secondary battery | |
| JPH0465070A (en) | All-solid-state voltage memory element | |
| JPS6151749A (en) | Nonaqueous electrolyte battery | |
| JPS61284061A (en) | Organic electrolyte battery | |
| JPH01246763A (en) | Nonaqueous solvent battery | |
| JPH0355029B2 (en) | ||
| JPH01274358A (en) | Organic electrolyte secondary battery | |
| JPH0520862B2 (en) | ||
| JPS60198068A (en) | solid electrolyte secondary battery | |
| JPH0320861B2 (en) |