JPH01294357A - Positive electrode for nonaqueous lithium secondary battery - Google Patents
Positive electrode for nonaqueous lithium secondary batteryInfo
- Publication number
- JPH01294357A JPH01294357A JP63125148A JP12514888A JPH01294357A JP H01294357 A JPH01294357 A JP H01294357A JP 63125148 A JP63125148 A JP 63125148A JP 12514888 A JP12514888 A JP 12514888A JP H01294357 A JPH01294357 A JP H01294357A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- titanium disulfide
- particle size
- energy density
- lithium secondary
- 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 abstract description 18
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RXKSUMQTYBHJHU-UHFFFAOYSA-N [S-2].[S-2].S.[Ti+4] Chemical compound [S-2].[S-2].S.[Ti+4] RXKSUMQTYBHJHU-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 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
- 239000007789 gas Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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)
- Inorganic Chemistry (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、正極活物質に二硫化チタンを用いた非水リチ
ウム二次電池の正極に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a positive electrode for a non-aqueous lithium secondary battery using titanium disulfide as a positive electrode active material.
従来の技術
負極にリチウムやリチウム合金、電解液に有機溶媒を用
いた非水リチウム二次電池は、金属の酸化物やカルコゲ
ン化合物を活物質とする正極と組み合わせることにより
、既存の鉛蓄電池やアルカリ蓄電池に比べて飛躍的に大
きなエネルギー密度を得ることが可能であるためにその
実現が待たれている。Conventional technology Non-aqueous lithium secondary batteries, which use lithium or lithium alloys for the negative electrode and organic solvents for the electrolyte, can be used in combination with positive electrodes that use metal oxides or chalcogen compounds as active materials, making them easier to use than existing lead-acid batteries or alkaline batteries. Its realization is eagerly awaited because it is possible to obtain dramatically higher energy density than storage batteries.
非水リチウム二次電池用正極活物質とじては非常に多種
のものが、提案されているが、なかでも二硫化チタン（
Ｔｉｅ、 ）を活物質として用いた正極は、充放電の繰
り返しに対する容量の安定性が極めて優れているなめに
最も有望であるとされている。A wide variety of positive electrode active materials for nonaqueous lithium secondary batteries have been proposed, but titanium disulfide (
A positive electrode using Tie, ) as an active material is said to be the most promising because it has extremely excellent capacity stability against repeated charging and discharging.
二硫化チタンの充放電反応は、下記の式で示すように、
放電時には層状化合物であるＴｉＳ、の層間に［ｉがイ
ンターカレーションし、充電時には二硫化チタン層間よ
りリチウムが抜は出し負極に析出するというものである
。The charging and discharging reaction of titanium disulfide is as shown by the following formula:
During discharging, [i intercalates between the layers of TiS, which is a layered compound, and during charging, lithium is extracted from between the titanium disulfide layers and deposited on the negative electrode.
ｘＬｉ ＋ Ｔｉ５ｚ ＹＬｉ、Ｔｉ５２（Ｘ≦１）こ
のＴ ｉｓ、に出入りするリチウムが多い程正極のエネ
ルギー密度（容量）は大きくなる。出入りするリチウム
の量は二硫化チタン１モルに対しリチウム１モルを最大
とし、Ｔｉと Ｓの化学量論比によって決まるといわれ
ている。すなわち、二硫化チタンは通常Ｔｉが化学量論
比よりも大きい側にずれる傾向があり、ずれが大きい程
インター力レ−ジョンするリチウムの量は１より小さく
なる。したがって、二硫化チタンの化学量論比がずれな
いようにするために、従来より二硫化チタンの合成方法
が検討されてきた。xLi + Ti5z YLi, Ti52 (X≦1) The more lithium that goes in and out of this Tis, the greater the energy density (capacity) of the positive electrode. The amount of lithium that goes in and out is determined by the stoichiometric ratio of Ti and S, with a maximum of 1 mole of lithium per mole of titanium disulfide. That is, in titanium disulfide, Ti usually tends to shift to the side where the Ti ratio is larger than the stoichiometric ratio, and the larger the shift, the smaller the amount of lithium that undergoes interforce formation becomes less than 1. Therefore, in order to prevent the stoichiometric ratio of titanium disulfide from shifting, methods for synthesizing titanium disulfide have been studied.
発明が解決しようとする課題
非水リチウム二次電池用正極活物質として二硫化チタン
を用いた正極は、充放電の繰り返しに対する寿命特性は
非常に優れているが、平均放電電圧は２．１ｖであり、
二酸化マンガンやバナジウム酸化物等を用いた正極（平
均放電電圧は３ｖに近い）と比べてエネルギー密度は若
干少なく、二硫化チタンの化学量論比の検討のみでは不
十分であった。Problems to be Solved by the Invention A positive electrode using titanium disulfide as a positive electrode active material for a non-aqueous lithium secondary battery has very good life characteristics against repeated charging and discharging, but the average discharge voltage is 2.1V. can be,
The energy density is slightly lower than that of positive electrodes using manganese dioxide, vanadium oxide, etc. (average discharge voltage is close to 3 V), and examination of the stoichiometric ratio of titanium disulfide alone was insufficient.
課題を解決するための手段
本発明では二硫化チタン、導電性粉末、結着剤の混合物
を集電体に保持させた非水リチウム二次電池用正極にお
いて、粒径が３０μｍ未満の二硫化チタンを使うことを
特徴とするものであり、これによってよりエネルギー密
度の高い正極を得るものである。Means for Solving the Problems The present invention provides a positive electrode for a non-aqueous lithium secondary battery in which a current collector holds a mixture of titanium disulfide, conductive powder, and a binder. This method is characterized by the use of , thereby obtaining a positive electrode with higher energy density.
作用
二硫化チタンは、六方晶の結晶形を有し、個々の粒子の
形状は一般的にはａ軸方向に広がった六角形状で薄い板
状をしている。二硫化チタンを正極活物質として用いる
場合には前述したごとく化学量論比等、組成的な性状が
容量に影響を及ぼす一つの因子であるが、さらに二硫化
チタンの粒径が重要な因子であることを見出した。すな
わち二硫化チタンは主にいわゆるＣＶＤ法と呼ばれる塩
化チタン（ＴｉＣ１）と硫化水素（Ｈ２Ｓ）とを気相で
析出させる方法、または三硫化チタン（ＴｔＳｓ ）を
熱分解によって得る方法で合成される。Functional titanium disulfide has a hexagonal crystal form, and the shape of each individual particle is generally a hexagonal shape extending in the a-axis direction and a thin plate shape. When titanium disulfide is used as a positive electrode active material, compositional properties such as stoichiometric ratio are one of the factors that affect capacity, as mentioned above, but the particle size of titanium disulfide is an even more important factor. I discovered something. That is, titanium disulfide is mainly synthesized by a so-called CVD method in which titanium chloride (TiC1) and hydrogen sulfide (H2S) are precipitated in a gas phase, or by a method in which titanium trisulfide (TtSs) is obtained by thermal decomposition.
そこで、これらの合成方法を制御することによって種々
の粒径の異なる二硫化チタンを合成し、それぞれ粒径の
異なる二硫化チタンを用いて正極板を作り特性の違いを
調べた結果、正極の容量当たりのエネルギー密度は、粒
径により大きく変化することがわかった。Therefore, by controlling these synthesis methods, we synthesized titanium disulfide with various particle sizes, made positive electrode plates using titanium disulfide with different particle sizes, and investigated the differences in characteristics.As a result, we found that the capacity of the positive electrode It was found that the energy density per particle changes greatly depending on the particle size.
容量当たりのエネルギー密度は単位容積光たりの活物質
量とその利用率の積で決まるわけであるが、二硫化チタ
ンを使った正極では単位容積光たりの二硫化チタンの量
は、粒径の大きい方が相対的に多いが、一方その利用率
は粒径が１０〜２０μｍ程度で最大となる傾向がある。The energy density per capacity is determined by the product of the amount of active material per unit volume of light and its utilization rate, but in the case of a positive electrode using titanium disulfide, the amount of titanium disulfide per unit volume of light is determined by the particle size. Although the larger the particle size, the larger the amount, the utilization rate tends to be maximum when the particle size is about 10 to 20 μm.
これら両者の関係から、容量当たりのエネルギー密度の
高い正極を得るためには粒径３０μｍ未満の二硫化チタ
ンを用いることが好ましい。From the relationship between these two, it is preferable to use titanium disulfide with a particle size of less than 30 μm in order to obtain a positive electrode with high energy density per capacity.
実施例 次に本発明を好適な実施例を用いて説明する。Example Next, the present invention will be explained using preferred embodiments.
三硫化チタンの熱分解で合成した二硫化チタン粉末な粒
径毎にふるい分けし、それぞれの粒径の二硫化チタンを
用いて次の条件で正極を作った。Titanium disulfide powder synthesized by thermal decomposition of titanium trisulfide was sieved by particle size, and positive electrodes were made using titanium disulfide of each particle size under the following conditions.
二硫化チタン９０部、アセチレンブラック１０部。90 parts of titanium disulfide, 10 parts of acetylene black.
ポリテトラフルオロエチレン粉末１０部の混合物０゜１
２ｇを、厚さ０．１１１１のニッケル板を加工して作っ
た１０Ｘ １０１１１１のエクスパンデッドメタルに充
填し、５００ｋｇ／ｃｎ２の圧力で加圧成形した。Mixture of 10 parts of polytetrafluoroethylene powder 0°1
2 g was filled into a 10×101111 expanded metal made by processing a nickel plate with a thickness of 0.1111, and pressure molded at a pressure of 500 kg/cn2.
次にリチウム板を相平衡とし、電解液にＬｉＡＳＦａを
１．５モル溶解したプロピレンカーボネート溶液を用い
て上記の正極の充放電を行い、その特性を調べた。尚、
充放電において電流密度は１ｎＡ／ｃｎ２、充電時の終
止電圧は２．８ｖ、放電時の終止電圧は１゜５ｖとした
。Next, with the lithium plate in phase equilibrium, the above positive electrode was charged and discharged using a propylene carbonate solution containing 1.5 moles of LiASFa dissolved in the electrolytic solution, and its characteristics were investigated. still,
During charging and discharging, the current density was 1 nA/cn2, the final voltage during charging was 2.8 V, and the final voltage during discharging was 1°5 V.
第１表に放電容量およびエネルギー密度の結果をまとめ
て示す。Table 1 summarizes the results of discharge capacity and energy density.
第１表
第１表から明らかなように、大きな粒径のものを用いた
極板程厚みは小さく理論エネルギー密度は大きい、しか
し実際の容量当たりのエネルギー密度は粒径が３０μｍ
未満の場合には３２０ｎＡｈ／ｃｃと高く、特に１０μ
ＩＩ以上２０ＡＬ１１未満では３３０ＩＩＡｈ／ＣＣと
最高となるが、３０μｍ以上になると急に減少している
。Table 1 As is clear from Table 1, the electrode plate using a larger particle size has a smaller thickness and a higher theoretical energy density, but the actual energy density per capacity is 30 μm when the particle size is 30 μm.
If it is less than 320nAh/cc, it is high, especially 10μ
It reaches a maximum of 330IIAh/CC when it is II or more and less than 20AL11, but it suddenly decreases when it becomes 30 μm or more.
次に第１表に示した各正極の放電電圧特性を第１図に示
した０本発明による粒径が３０μｍ未満の二硫化チタン
を用いた正極Ａ、ＢおよびＣはそれぞれ放電電圧が高く
放電時間も長いが、粒径が３０μｍ以上のものを用いた
正極りおよびＥでは放電電圧１時間とも大きく減少し、
本発明の正極に比べ特性的に大きく劣っていることがわ
かる。Next, the discharge voltage characteristics of each positive electrode shown in Table 1 are shown in Figure 1.The positive electrodes A, B, and C according to the present invention using titanium disulfide with a particle size of less than 30 μm each have a high discharge voltage. Although the time is long, in the positive electrode and E using particles with a particle size of 30 μm or more, the discharge voltage decreases significantly after 1 hour.
It can be seen that the characteristics are significantly inferior to the positive electrode of the present invention.
発明の効果
以上述べたように本発明により、放電量が大きく、容積
当たりの実際のエネルギー密度が高い非水リチウム二次
電池用正極を得ることができる。Effects of the Invention As described above, according to the present invention, it is possible to obtain a positive electrode for a non-aqueous lithium secondary battery that has a large discharge amount and a high actual energy density per volume.
第１図は、非水リチウム二次電池用正極の放電特性であ
る。
Ａ、Ｂ、Ｃ・・・本発明による正極
り、Ｅ・・・比較のための正極
嵜 １ 図
時間〔旧FIG. 1 shows the discharge characteristics of a positive electrode for a non-aqueous lithium secondary battery. A, B, C...Positive electrode according to the present invention, E...Positive electrode for comparison 1 Figure Time [Old
Claims (1)
体に保持してなる非水リチウム二次電池用正極において
、粒径が３０μｍ未満の二硫化チタンを使用したことを
特徴とする非水リチウム二次電池用正極。1. A positive electrode for a non-aqueous lithium secondary battery comprising a mixture of titanium disulfide, conductive powder, and a binder held in a conductor, characterized in that titanium disulfide with a particle size of less than 30 μm is used. Positive electrode for non-aqueous lithium secondary batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125148A JPH01294357A (en) | 1988-05-23 | 1988-05-23 | Positive electrode for nonaqueous lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125148A JPH01294357A (en) | 1988-05-23 | 1988-05-23 | Positive electrode for nonaqueous lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01294357A true JPH01294357A (en) | 1989-11-28 |
Family
ID=14903055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63125148A Pending JPH01294357A (en) | 1988-05-23 | 1988-05-23 | Positive electrode for nonaqueous lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01294357A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654281A (en) * | 1986-03-24 | 1987-03-31 | W. R. Grace & Co. | Composite cathodic electrode |
| JPS63250055A (en) * | 1986-03-24 | 1988-10-17 | ミネソタ・マイニング・アンド・マニュファクチャリング・カンパニー | Cathode |
-
1988
- 1988-05-23 JP JP63125148A patent/JPH01294357A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654281A (en) * | 1986-03-24 | 1987-03-31 | W. R. Grace & Co. | Composite cathodic electrode |
| JPS63250055A (en) * | 1986-03-24 | 1988-10-17 | ミネソタ・マイニング・アンド・マニュファクチャリング・カンパニー | Cathode |
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