JPS6331899B2 - - Google Patents
Info
- Publication number
- JPS6331899B2 JPS6331899B2 JP54161873A JP16187379A JPS6331899B2 JP S6331899 B2 JPS6331899 B2 JP S6331899B2 JP 54161873 A JP54161873 A JP 54161873A JP 16187379 A JP16187379 A JP 16187379A JP S6331899 B2 JPS6331899 B2 JP S6331899B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- active material
- electrode active
- positive electrode
- 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 16
- 239000005751 Copper oxide Substances 0.000 claims description 16
- 229910000431 copper oxide Inorganic materials 0.000 claims description 16
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 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
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- -1 polypropylene Polymers 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
- 239000007787 solid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
本発明はリチウム又はリチウム合金を負極活物
質とする非水電解液電池に係り、特に正極活物質
の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous electrolyte battery using lithium or a lithium alloy as a negative electrode active material, and particularly to improvements in the positive electrode active material.
この種電池の正極活物質としては金属の酸化物
硫化物、弗化物等種々のものが提案されているが
金属酸化物の中でも酸化銅は活物質としての容量
が大きく比較的安価で資源的にも豊富であり、非
水電解液電池の正極活物質として注目されてい
る。又酸化銅一リチウム系非水電解液電池はその
放電安定電圧が二酸化マンガンやフツ化炭素系の
リチウム電池の約半分程度であるが、汎用の酸化
銀電池や水銀電池と互換使用するためにはその放
電電圧が1.2〜1.3Vと若干低い問題がある。 Various metal oxides such as sulfides and fluorides have been proposed as positive electrode active materials for this type of battery, but among metal oxides, copper oxide has a large capacity as an active material, is relatively inexpensive, and is resource-friendly. It is also abundant and is attracting attention as a positive electrode active material for non-aqueous electrolyte batteries. In addition, the stable discharge voltage of monolithium copper oxide non-aqueous electrolyte batteries is about half that of manganese dioxide or carbon fluoride lithium batteries, but in order to be used interchangeably with general-purpose silver oxide batteries and mercury batteries, There is a problem that the discharge voltage is slightly low at 1.2 to 1.3V.
本発明は金属板を母体とし部分的に酸化銅及び
硫化銅を形成したるものを正極活物質として用い
ることを特徴とし、放電電圧特性を改善して汎用
電池と互換性良好な非水電解液電池を提供するこ
とを目的とするものである。 The present invention is characterized by using a metal plate as a matrix and partially forming copper oxide and copper sulfide as a positive electrode active material, and is a non-aqueous electrolyte with improved discharge voltage characteristics and good compatibility with general-purpose batteries. The purpose is to provide batteries.
以下本発明の実施例を説明する。 Examples of the present invention will be described below.
純度99.9％の金属銅粉末100ｇと、硫黄粉末50
ｇとを乳鉢で混合する。この混合物をアルミナボ
ート中に入れた状態で酸素ガスを500ml／分供給
せる電気炉内において500℃で10時間加熱反応さ
せる。冷却後、この固型物を乳鉢で粉砕して400
メツシユのふるいを通過させる。このようにして
得られた活物質粒子は第１図に示す如く金属銅Ａ
を母体とし部分的に酸化銅Ｂ及び硫化銅Ｃが形成
されている。 100g of 99.9% pure copper powder and 50g of sulfur powder
g in a mortar. This mixture was placed in an alumina boat and reacted by heating at 500° C. for 10 hours in an electric furnace to which oxygen gas could be supplied at 500 ml/min. After cooling, crush this solid in a mortar and
Pass through a mesh sieve. The active material particles thus obtained are made of metallic copper A as shown in FIG.
Copper oxide B and copper sulfide C are partially formed from the base material.
正極はこの活物質粉末に導電剤としての炭素粉
末及び弗素樹脂を90：２：２（重量％）の比で混
合し、この混合物を極板寸法に加圧成型後300℃
で熱結着する。 The positive electrode is made by mixing this active material powder with carbon powder and fluororesin as a conductive agent in a ratio of 90:2:2 (wt%), and press-molding this mixture into an electrode plate size at 300℃.
Thermal bonding is performed.
負極はリチウム圧延板を極板寸法に打抜き、電
解液は１モル濃度の過塩素酸リチウムをプロピレ
ンカーボネイトと1.2−ジメトキシエタンとの混
合溶媒に溶解してポリプロピレン不織布よりなる
セパレータに含浸し、直径11.6mm高さ5.4mmのボ
タン型電池を組立てた。 The negative electrode was made by punching a rolled lithium plate to the plate dimensions, and the electrolytic solution was prepared by dissolving 1 molar concentration of lithium perchlorate in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane and impregnating it into a separator made of polypropylene nonwoven fabric. A button-type battery with a height of 5.4 mm was assembled.
第２図は本発明電池の5.6KΩ定負荷放電特
性を示すものであり、，は比較のため正極活
物質として夫々酸化銅及び硫化銅を単独で用いた
電池の場合である。又、は正極活物質として酸
化銅と硫化銅との単なる混合物を用いた電池の場
合である。 FIG. 2 shows the 5.6KΩ constant load discharge characteristics of the battery of the present invention, and for comparison, , is the case of a battery using copper oxide and copper sulfide alone as positive electrode active materials, respectively. Also, is the case of a battery using a simple mixture of copper oxide and copper sulfide as the positive electrode active material.
この特性図に見られるように本発明電池は酸化
銅或いは硫化銅単独の電池の中間の1.4〜1.5Vの
放電電圧を示し、酸化銅単独の場合より放電電圧
が引上げられていると共に硫化銅単独の場合にお
ける二段階放電電圧も解消されている。 As seen in this characteristic diagram, the battery of the present invention exhibits a discharge voltage of 1.4 to 1.5 V, which is between 1.4 to 1.5 V, which is between the batteries using copper oxide or copper sulfide alone, and the discharge voltage is higher than that of copper oxide alone. The two-stage discharge voltage in the case of is also eliminated.
このように放電電圧が引上げられる理由は本発
明電池の正極活物質が酸化銅と硫化銅との混成電
位を生じるためであると考えられる。 The reason why the discharge voltage is increased in this way is considered to be that the positive electrode active material of the battery of the present invention generates a mixed potential of copper oxide and copper sulfide.
酸化銅と硫化銅との単なる混合物を正極活物質
とした場合には第２図のの特性から明らかなよ
うに二段階の放電電圧を示す。これは酸化銅と硫
化銅とが夫々粒子として分離した状態で存在し、
硫化銅の方が優先的に放電されるためである。 When a simple mixture of copper oxide and copper sulfide is used as the positive electrode active material, two stages of discharge voltage are exhibited as is clear from the characteristics of FIG. This is because copper oxide and copper sulfide each exist in a separated state as particles,
This is because copper sulfide is preferentially discharged.
又、導電性が低い酸化銅と硫化銅の各粒子間の
接触抵抗は大きく導電性に難があり、そのため電
圧が下がつたり放電電圧特性が不安定になる懸念
がある。 In addition, the contact resistance between each particle of copper oxide and copper sulfide, which have low conductivity, is large and conductivity is difficult, so there is a concern that the voltage may drop and the discharge voltage characteristics may become unstable.
これに対して、本発明電池の正極活物質は金属
銅を母体とし部分的に酸化銅及び硫化銅が形成さ
れたものであり、同一粒子内に酸化銅及び硫化銅
が混在しているため混成電位が生じ平担な放電電
圧特性が得られる。 On the other hand, the positive electrode active material of the battery of the present invention is made of metallic copper as a matrix with copper oxide and copper sulfide partially formed, and is a hybrid because copper oxide and copper sulfide are mixed in the same particle. A potential is generated and a flat discharge voltage characteristic is obtained.
又、導電性についても各粒子の一部に露出せる
金属銅の存在により、この金属銅を介して粒子間
が接触するため粒子間の接触抵抗は低く仰えられ
導電性が向上する。 Regarding conductivity, due to the presence of metallic copper exposed in a portion of each particle, the particles come into contact via the metallic copper, so the contact resistance between the particles can be said to be low, and the electrical conductivity is improved.
上述した如く、金属銅を母体とし部分的に酸化
銅及び硫化銅を形成したるものを正極活物質とし
て用いた本発明非水電解液電池は放電電圧が1.4
〜1.5Vで安定化し、汎用されている酸化銀電池
や水銀電池と互換使用する場合に極めて有益なる
ものである。 As mentioned above, the non-aqueous electrolyte battery of the present invention, which uses metallic copper as a matrix and partially forms copper oxide and copper sulfide as the positive electrode active material, has a discharge voltage of 1.4.
It is stabilized at ~1.5V and is extremely useful when used interchangeably with commonly used silver oxide batteries and mercury batteries.
第１図は本発明電池の正極活物質粒子の模式図
第２図は本発明電池の放電特性を従来電池と比較
して示す図である。
Ａ……金属銅、Ｂ……酸化銅、Ｃ……硫化銅。
FIG. 1 is a schematic diagram of the positive electrode active material particles of the battery of the present invention. FIG. 2 is a diagram showing the discharge characteristics of the battery of the present invention in comparison with a conventional battery. A...metallic copper, B...copper oxide, C...copper sulfide.
Claims (1)
し、金属銅を母体とし部分的に酸化銅及び硫化銅
を形成したるものを正極活物質とする非水電解液
電池。1. A nonaqueous electrolyte battery that uses lithium or a lithium alloy as a negative electrode active material and a positive electrode active material that uses metallic copper as a matrix and partially forms copper oxide and copper sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16187379A JPS5684877A (en) | 1979-12-12 | 1979-12-12 | Battery with nonaqueous electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16187379A JPS5684877A (en) | 1979-12-12 | 1979-12-12 | Battery with nonaqueous electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5684877A JPS5684877A (en) | 1981-07-10 |
| JPS6331899B2 true JPS6331899B2 (en) | 1988-06-27 |
Family
ID=15743588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16187379A Granted JPS5684877A (en) | 1979-12-12 | 1979-12-12 | Battery with nonaqueous electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5684877A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5857262A (en) * | 1981-09-30 | 1983-04-05 | Toshiba Corp | Positive electrode of organic solvent battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS589957A (en) * | 1981-07-10 | 1983-01-20 | Mitsubishi Metal Corp | Material for cutting tool with superior characteristic at high temperature |
-
1979
- 1979-12-12 JP JP16187379A patent/JPS5684877A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS589957A (en) * | 1981-07-10 | 1983-01-20 | Mitsubishi Metal Corp | Material for cutting tool with superior characteristic at high temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5684877A (en) | 1981-07-10 |
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