JPS62222568A - Manufacture of lithium battery - Google Patents
Manufacture of lithium batteryInfo
- Publication number
- JPS62222568A JPS62222568A JP61063770A JP6377086A JPS62222568A JP S62222568 A JPS62222568 A JP S62222568A JP 61063770 A JP61063770 A JP 61063770A JP 6377086 A JP6377086 A JP 6377086A JP S62222568 A JPS62222568 A JP S62222568A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- organic solvent
- electrode active
- positive
- 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.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 15
- 229910052744 lithium Inorganic materials 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000007774 positive electrode material Substances 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- PUHFCVOTRFZSPR-KVVVOXFISA-N (z)-octadec-9-enamide;oxirane Chemical compound C1CO1.CCCCCCCC\C=C/CCCCCCCC(N)=O PUHFCVOTRFZSPR-KVVVOXFISA-N 0.000 claims abstract description 9
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims abstract description 3
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 2
- BITAPBDLHJQAID-KTKRTIGZSA-N 2-[2-hydroxyethyl-[(z)-octadec-9-enyl]amino]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCN(CCO)CCO BITAPBDLHJQAID-KTKRTIGZSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 13
- -1 oleoyl diethanol amine Chemical compound 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000010287 polarization Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229940043237 diethanolamine Drugs 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 description 13
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 2
- 229910000807 Ga alloy Inorganic materials 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- VRSMQRZDMZDXAU-UHFFFAOYSA-N bis(sulfanylidene)niobium Chemical compound S=[Nb]=S VRSMQRZDMZDXAU-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910013888 LiPF5 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WCQOLGZNMNEYDX-UHFFFAOYSA-N bis(selanylidene)vanadium Chemical compound [Se]=[V]=[Se] WCQOLGZNMNEYDX-UHFFFAOYSA-N 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 1
- WVMYSOZCZHQCSG-UHFFFAOYSA-N bis(sulfanylidene)zirconium Chemical compound S=[Zr]=S WVMYSOZCZHQCSG-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 229910000339 iron disulfide Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はリチウム電池の製造方法に係り、さらに詳しく
はその正極の改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a lithium battery, and more particularly to improvement of a positive electrode thereof.
従来、リチウム電池の正極は、正￥ＦＡ活物質粉末を加
圧成形するか、あるいは正極活物質粉末に結着剤として
ポリテトラフルオロエチレン粉末を添加、混合した正極
合剤を加圧成形することによって作製されていた（例え
ば特開昭５５−１４６８８０号公報）。Conventionally, positive electrodes for lithium batteries have been made by pressure molding positive FA active material powder, or by pressure molding a positive electrode mixture in which polytetrafluoroethylene powder is added and mixed as a binder to positive electrode active material powder. (for example, Japanese Patent Laid-Open No. 146880/1983).
ところが、二硫化チタンなどの正極活物質は有機溶媒と
のなじみが悪く、また結着剤として用いられるポリテト
ラフルオロエチレン粉末も有機溶媒に対するなじみが悪
いため、正極活物質の粒子表面が部分的にしか電解液に
濡れず、そのため正極活物質粒子の全表面を電池反応に
利用することができず、正極活物質の粒子表面中、電解
液に濡れた部分だけが電池反応に関与するため、電流書
度が高くなり、その結果、分極が大きくなって、正極の
利用率が低下するという問題があった。However, positive electrode active materials such as titanium disulfide have poor compatibility with organic solvents, and polytetrafluoroethylene powder used as a binder also has poor compatibility with organic solvents, so the particle surface of the positive electrode active material partially Therefore, the entire surface of the positive electrode active material particle cannot be used for the battery reaction, and only the part of the positive electrode active material particle surface that is wet with the electrolyte participates in the battery reaction, so the current There is a problem in that the degree of writing becomes high, and as a result, polarization becomes large and the utilization rate of the positive electrode decreases.
本発明は、正極活物質粉末または正極を有機溶媒に可溶
な界面活性剤で処理して正極活物質の粒子表面に親有機
溶媒性を付与することによって、正極活物質の粒子表面
を広い面禎で電池反応に利用できるようにして、電流密
度を下げ、正極の利用率を向上させたものである。In the present invention, the particle surface of the positive electrode active material can be spread over a wide area by treating the positive electrode active material powder or the positive electrode with a surfactant soluble in an organic solvent to impart organophilic properties to the particle surface of the positive electrode active material. This makes it possible to use it for battery reactions, lowering the current density and improving the utilization rate of the positive electrode.
正極活物質粉末または正極の界面活性剤処理にあたり、
界面活性剤としては、例えばオレイン酸アミドエチレン
オキサイド付加物、オレイン酸アミド、オレイン酸ジェ
タノールアミド、オレイルジェタノールアミンやそれら
の混合物が好用される。これは、これらの界面活性剤が
正極活物質の粒子表面に親有機溶媒性を付与するという
性質を有することはもとより、有機溶媒に可溶であって
、処理時に正極活物質に悪影曾を及ぼす水を使わなくて
済み、かつ電池内に残存しても電池性能に悪影響を及ぼ
すことが少ないからである。When treating the positive electrode active material powder or positive electrode with a surfactant,
As the surfactant, for example, oleic acid amide ethylene oxide adduct, oleic acid amide, oleic acid jetanolamide, oleyl jetanolamine, and mixtures thereof are preferably used. This is because these surfactants not only have the property of imparting organophilic properties to the particle surface of the positive electrode active material, but also are soluble in organic solvents and do not have an adverse effect on the positive electrode active material during processing. This is because it eliminates the need to use water that causes harmful effects, and even if water remains in the battery, it has little negative effect on battery performance.
処理にあたっては、界面活性剤は有機溶媒に溶解するか
、または有機溶媒を電解液溶媒として用いる電解液に熔
解される。その際の濃度としては、０．５〜５重量％に
するのが好ましい。有ｉ熔媒としては、界面活性剤を溶
解する能力を持つものであれば特に限定されることなく
、各種のものを用い（するが、電解液の溶媒として用い
ることができるものであれば、処理後の除去を要しない
ので、特に好都合である。In processing, the surfactant is dissolved in an organic solvent or in an electrolyte using an organic solvent as the electrolyte solvent. The concentration at that time is preferably 0.5 to 5% by weight. As the solvent, there are no particular limitations, and various solvents can be used as long as they have the ability to dissolve the surfactant (however, as long as they can be used as a solvent for the electrolytic solution, This is particularly advantageous since no post-processing removal is required.
界面活性剤による処理は、例えば正極活物質粉末を界面
活性剤を溶解した有機溶媒溶液に浸漬するか、あるいは
正極（なお、ここで正極とは、正極活物質の加圧成形体
または正極活物質に結着剤や導電助剤などの添加剤を添
加、混合した正極合剤の加圧成形体をいう）を界面活性
剤を溶解した電解液と共に電池組立に供し、電池内で正
極活物質と界面活性剤とが接触して処理が進行するよう
に行われる。もとより、正極活物質粉末を界面活性剤を
熔解した電解液に浸漬してもよいし、また、正極を界面
活性剤を溶解した有機溶媒中に浸漬したのち、通常の電
池組立を行ってもよい。The treatment with a surfactant can be carried out, for example, by immersing the positive electrode active material powder in an organic solvent solution in which the surfactant is dissolved, or by immersing the positive electrode active material powder in an organic solvent solution containing a surfactant, or by immersing the positive electrode active material powder in a positive electrode (here, the positive electrode refers to a pressure-molded product of the positive electrode active material or a positive electrode active material). A press-molded body of a positive electrode mixture prepared by adding and mixing additives such as a binder and a conductive aid) is used for battery assembly together with an electrolyte in which a surfactant is dissolved, and the positive electrode active material and the mixture are mixed together in the battery. The treatment is carried out in such a way that the treatment progresses through contact with the surfactant. Of course, the positive electrode active material powder may be immersed in an electrolytic solution in which a surfactant is dissolved, or the positive electrode may be immersed in an organic solvent in which a surfactant is dissolved, and then normal battery assembly may be performed. .
処理後、溶媒が電解液溶媒または電解液である場合には
、ことさら溶媒の除去をする必要がなく、正極活物質粉
末を湿潤状態のままで加圧成形に供してもよいし、また
、前記したように正極を界面活性剤を熔解した電解液と
共に電池組立に供し、電池内で正極を界面活性剤で処理
してもよい。After the treatment, if the solvent is an electrolytic solution solvent or an electrolytic solution, there is no need to particularly remove the solvent, and the positive electrode active material powder may be subjected to pressure molding in a wet state. As described above, the positive electrode may be subjected to battery assembly together with an electrolytic solution in which a surfactant is dissolved, and the positive electrode may be treated with the surfactant within the battery.
電解液には、通常、１．２−ジメトキシエタン、Ｌ２−
ジェトキシエタン、プロピレンカーボネート、Ｔ−ブチ
ロラクトン、エチレンカーボネート、テトラヒドロフラ
ン、２−メチル−テトラヒドロフラン、１，３−ジオキ
ソラン、４−メチル−１，３−ジオキソランの単独また
は２種以上の混合溶媒を電解液溶媒とし、これに例えば
ＬｉＣＩＯ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＳｂＦ
６、Ｌｉｌ３Ｆ４、Ｌ ｉＢ （Ｃｓ Ｈ５）４などの
電解質を熔解した有機電解液が用いられる。また、上記
電解液中におけるＬｉＰＦ６などの電解質を安定化させ
るために、例えばヘキサメチルホスホリックトリアミド
などの安定化剤を電解液中に加えておくことも好ましく
採用される。そして、前述したような観点から、界面活
性剤を溶解する有機溶媒を選択するにあたっては、上記
例示の電解液溶媒の中から採用するのが好ましい。The electrolyte usually contains 1,2-dimethoxyethane, L2-
Jetoxyethane, propylene carbonate, T-butyrolactone, ethylene carbonate, tetrahydrofuran, 2-methyl-tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane alone or in a mixture of two or more as the electrolyte solvent, For example, LiCIO4, LiPF6, LiAsF6, LiSbF
6, an organic electrolyte solution in which an electrolyte such as Lil3F4 or LiB (Cs H5)4 is dissolved is used. Further, in order to stabilize the electrolyte such as LiPF6 in the electrolytic solution, it is also preferably employed to add a stabilizer such as hexamethylphosphoric triamide to the electrolytic solution. From the above-mentioned viewpoint, when selecting an organic solvent for dissolving the surfactant, it is preferable to select an organic solvent from among the above-mentioned exemplified electrolyte solution solvents.
正極活物質としては、例えば二硫化チタン（Ｔｉｓ２）
、二硫化モリブデン（ＭＯ３２）、三硫化モリブデン（
ＭＯ３３）、二硫化鉄（ＦｅＳ２）、硫化ジルコニウム
（ＺｒＳ２）、二硫化ニオブ（ＮｂＳ２）、三硫化リン
ニッケル（ＮｉＰＳ３）、バナジウムセレナイド（ＶＳ
ｅ２）、五酸化バナジウム（■２ｏ５）、十三酸化バナ
ジウム（Ｖ６Ｏ１３）などが用いられる。また、負極に
はリチウムまたはリチウム合金が用いられる。上記リチ
ウム合金としては、例えばリチウム−アルミニウム合金
、リチウム−鉛合金、リチウム−インジウム合金、リチ
ウム−ガリウム合金、リチウム−インジウム−ガリウム
合金、リチウム−マグネシウム合金、リチウム−亜鉛合
金などが用いられる。As the positive electrode active material, for example, titanium disulfide (Tis2)
, molybdenum disulfide (MO32), molybdenum trisulfide (
MO33), iron disulfide (FeS2), zirconium sulfide (ZrS2), niobium disulfide (NbS2), nickel phosphorus trisulfide (NiPS3), vanadium selenide (VS
e2), vanadium pentoxide (■2o5), vanadium trioxide (V6O13), etc. are used. Furthermore, lithium or a lithium alloy is used for the negative electrode. Examples of the lithium alloy used include lithium-aluminum alloy, lithium-lead alloy, lithium-indium alloy, lithium-gallium alloy, lithium-indium-gallium alloy, lithium-magnesium alloy, and lithium-zinc alloy.
つぎに実施例をあげて本発明をさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例に
硫化チタン粉末をオレイン酸アミドエチレンオキサイド
付加物を溶解したプロピレンカーボネート溶液（オレイ
ン酸アミドエチレンオキサイド付加物の濃度：２重量％
）に浸漬した後、Ｌ１ｍＡｈ相当量秤取し、これにポリ
テトラフルオロエチレン粉末を５重量％添加して混合し
た後、金型に充填し、１００ｋｇ／ａＪの圧力で加圧成
形して直径７ｍｏｗ、厚さ０．５ｍｍの正極を作製した
。In an example, titanium sulfide powder was dissolved in a propylene carbonate solution containing an oleic acid amide ethylene oxide adduct (concentration of oleic acid amide ethylene oxide adduct: 2% by weight).
), weighed out an amount equivalent to L1mAh, added 5% by weight of polytetrafluoroethylene powder and mixed it, then filled it into a mold and pressure-molded it at a pressure of 100kg/aJ to form a diameter of 7mow. , a positive electrode with a thickness of 0.5 mm was produced.
この正極と、負極にはリチウムを用い、電解液には４−
メチル−１，３−ジオキソランと１．２−ジメトキシエ
タンとヘキサメチルホスホリックトリアミドの容量比６
０：３５：５の混合溶媒にＬｉＰＦ５をｌｎ＋ｏｌ／Ａ
熔解した有機電解液を用いて、第１図に示す構造のリチ
ウム電池を作製した。Lithium is used for this positive electrode and negative electrode, and 4-
Volume ratio of methyl-1,3-dioxolane, 1,2-dimethoxyethane and hexamethylphosphoric triamide 6
LiPF5 in a mixed solvent of 0:35:5 ln+ol/A
A lithium battery having the structure shown in FIG. 1 was manufactured using the molten organic electrolyte.
第１図において、１は負極で、前述のようにリチウムか
らなり、２は前述のように界面活性剤（オレイン酸アミ
ドエチレンオキサイド付加物）で処理した二硫化チタン
を正極活物質として用いた正極である。３は前述の電解
液であり、４は微孔性ポリプロピレンフィルムからなる
セパレータで、５はポリプロピレン不織布からなる電解
液吸収体である。６はポリプロピレン製の環状ガスゲッ
トで、７はステンレス鋼製で外面にニッケルメッキを施
した負極缶であり、８はステンレス鋼製で外面にニッケ
ルメンキを施した正極缶である。９はステンレス鋼製網
からなる負極側の簗電体である。In FIG. 1, 1 is a negative electrode made of lithium as described above, and 2 is a positive electrode using titanium disulfide treated with a surfactant (oleic acid amide ethylene oxide adduct) as a positive electrode active material as described above. It is. 3 is the aforementioned electrolytic solution, 4 is a separator made of a microporous polypropylene film, and 5 is an electrolytic solution absorber made of a polypropylene nonwoven fabric. 6 is an annular gas get made of polypropylene, 7 is a negative electrode can made of stainless steel with a nickel plated outer surface, and 8 is a positive electrode can made of stainless steel with a nickel plated outer surface. Reference numeral 9 denotes a negative electrode side electrical body made of stainless steel mesh.
実施例２
二硫化チタン粉末４６ｍｇにポリテトラフルオロエチレ
ン粉末３Ｉ１ｇを添加して混合し、これを金型に充填し
１００ ｋｇ ／ ｃｉの圧力で加圧成形して直径７１
ｍｍ、厚さ０，５ａ＋ｍの正極を作製した。Example 2 1 g of polytetrafluoroethylene powder 3I was added to 46 mg of titanium disulfide powder, mixed, filled into a mold, and press-molded at a pressure of 100 kg/ci to a diameter of 71 mm.
A positive electrode with a thickness of 0.5 mm and a thickness of 0.5 mm was produced.
電解液には実施例１と同様に４−メチル−１，３−ジオ
キソランと１．２−ジメトキシエタンとへキサメチルホ
スホリックトリアミドの容量比６０ ： ３５：５の混
合溶媒にＬｉＰＦ６を１ａ＋ｏｌ／ｊ！熔解したものを
用い、この電解液１００重量部に対してオレイン酸アミ
ドエチレンオキサイド付加物を１重量部の割合で加えて
熔解した。As in Example 1, the electrolyte was a mixed solvent of 4-methyl-1,3-dioxolane, 1,2-dimethoxyethane, and hexamethylphosphoric triamide in a volume ratio of 60:35:5, and 1a+ol/LiPF6. j! Using the melted product, oleic acid amide ethylene oxide adduct was added at a ratio of 1 part by weight to 100 parts by weight of this electrolytic solution, and the mixture was melted.
負極にはリチウムを用い、前記のように作製した正極と
上記のようにオレイン酸アミドエチレンオキサイド付加
物を添加した電解液とを用い、それ以外は実施例１と同
様にして、第１図に示す構造のリチウム電池を作製した
。Lithium was used as the negative electrode, the positive electrode prepared as described above, and the electrolytic solution to which the oleic acid amide ethylene oxide adduct was added as described above. A lithium battery with the structure shown was fabricated.
比較例１
電解液にオレイン酸アミドエチレンオキサイド付加物を
添加することを行わなかったほかは実施例２と同様にし
て第１図に示す構造のリチウム電池を作製した。Comparative Example 1 A lithium battery having the structure shown in FIG. 1 was produced in the same manner as in Example 2 except that the oleic acid amide ethylene oxide adduct was not added to the electrolytic solution.
上記のように作製した実施例１〜２の電池および比較例
１の電池を２５℃、放電電流０．７６ｍＡ （正極のみ
かけ表面積あたり２ｍＡ／ｃｄ）で放電したときの放電
特性を第２図に示す。Figure 2 shows the discharge characteristics when the batteries of Examples 1 and 2 and the battery of Comparative Example 1 produced as described above were discharged at 25°C and a discharge current of 0.76 mA (2 mA/cd per apparent surface area of the positive electrode). show.
第２図に示すように、実施例１および実施例２の電池は
、比較例１の電池に比べて、放電容量が大きかった。こ
れは、実施例では、界面活性剤で処理して正極活物質の
粒子表面に親有機溶媒性を付与したため、正極活物質の
電解液に対する濡れ性が改善され、正極活物質の粒子表
面が広い面積で放電反応に利用できるようになり、電流
密度が低くなって、分極が小さくなり、正極の利用率が
向上したためであると考えられる。As shown in FIG. 2, the batteries of Example 1 and Example 2 had larger discharge capacities than the battery of Comparative Example 1. This is because in the example, the particle surface of the positive electrode active material was treated with a surfactant to give organophilic properties to the particle surface of the positive electrode active material, so the wettability of the positive electrode active material to the electrolyte was improved and the particle surface of the positive electrode active material was wide. This is thought to be because the area became available for discharge reaction, the current density became lower, the polarization became smaller, and the utilization rate of the positive electrode improved.
以上説明したように、本発明では、正極活物質粉末また
は正極を有機溶媒に可溶な界面活性剤で処理することに
より、正極活物質の粒子表面に親有機溶媒性を付与する
ことによって、正極活物質の粒子表面を広い面積で電池
反応に利用できるようにして、電流密度を下げ、分極を
小さくして、正極の利用率を向上させることができた。As explained above, in the present invention, the positive electrode active material powder or the positive electrode is treated with a surfactant soluble in an organic solvent to impart organophilic properties to the particle surface of the positive electrode active material. By making a wide area of the particle surface of the active material available for battery reactions, we were able to lower the current density, reduce polarization, and improve the utilization rate of the positive electrode.
第１図は本発明に係るリチウム電池の一例を示す断面図
であり、第２図は実施例１〜２の電池と比較例１の電池
の放電特性を示す図である。
１・・・負極、 ２・・・正極、 ３・・・電解液蒸１
閉
第 ２閏
放電容量（ｍＡｈ）FIG. 1 is a sectional view showing an example of a lithium battery according to the present invention, and FIG. 2 is a diagram showing the discharge characteristics of the batteries of Examples 1 and 2 and the battery of Comparative Example 1. 1... Negative electrode, 2... Positive electrode, 3... Electrolyte vapor 1
Closed 2nd leap discharge capacity (mAh)
Claims (3)
たは正極を有機溶媒に可溶な界面活性剤で処理して、正
極活物質の粒子表面に親有機溶媒性を付与することを特
徴とするリチウム電池の製造方法。(1) In the production of lithium batteries, a lithium battery characterized by treating the positive electrode active material powder or the positive electrode with a surfactant soluble in an organic solvent to impart organophilic solvent properties to the particle surface of the positive electrode active material. How to manufacture batteries.
第１項記載のリチウム電池の製造方法。(2) The method for manufacturing a lithium battery according to claim 1, wherein the positive electrode active material is titanium disulfide.
ド付加物、オレイン酸アミド、オレイン酸ジエタノール
アミドおよびオレイルジエタノールアミンよりなる群か
ら選ばれた少なくとも１種である特許請求の範囲第１項
または第２項記載のリチウム電池の製造方法。(3) Claim 1 or 2, wherein the surfactant is at least one selected from the group consisting of oleic acid amide ethylene oxide adduct, oleic acid amide, oleic acid diethanolamide, and oleyl diethanolamine. lithium battery manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61063770A JPS62222568A (en) | 1986-03-20 | 1986-03-20 | Manufacture of lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61063770A JPS62222568A (en) | 1986-03-20 | 1986-03-20 | Manufacture of lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62222568A true JPS62222568A (en) | 1987-09-30 |
Family
ID=13238936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61063770A Pending JPS62222568A (en) | 1986-03-20 | 1986-03-20 | Manufacture of lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62222568A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100445434B1 (en) * | 2002-07-10 | 2004-08-21 | 삼성에스디아이 주식회사 | Positive active material composition for lithium sulfur battery and lithium sulfur battery fabricated using same |
| US6872489B2 (en) * | 2002-02-27 | 2005-03-29 | Rovcal, Inc. | Alkaline cell with gassing inhibitors |
| JP2006302617A (en) * | 2005-04-19 | 2006-11-02 | Nissan Motor Co Ltd | Manufacturing method of electrode for secondary battery |
| US7226696B2 (en) | 2002-02-27 | 2007-06-05 | Rayovac Corporation | Alkaline cell with performance enhancing additives |
-
1986
- 1986-03-20 JP JP61063770A patent/JPS62222568A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6872489B2 (en) * | 2002-02-27 | 2005-03-29 | Rovcal, Inc. | Alkaline cell with gassing inhibitors |
| US7169504B2 (en) | 2002-02-27 | 2007-01-30 | Rovcal, Inc. | Alkaline cell with performance enhancing additives |
| US7226696B2 (en) | 2002-02-27 | 2007-06-05 | Rayovac Corporation | Alkaline cell with performance enhancing additives |
| US7749654B2 (en) | 2002-02-27 | 2010-07-06 | Rovcal, Inc. | Alkaline cell with performance enhancing additives |
| US8691439B2 (en) | 2002-02-27 | 2014-04-08 | Spectrum Brands, Inc. | Alkaline cell with performance enhancing additives |
| KR100445434B1 (en) * | 2002-07-10 | 2004-08-21 | 삼성에스디아이 주식회사 | Positive active material composition for lithium sulfur battery and lithium sulfur battery fabricated using same |
| JP2006302617A (en) * | 2005-04-19 | 2006-11-02 | Nissan Motor Co Ltd | Manufacturing method of electrode for secondary battery |
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