JPH0744042B2 - Electrolyte for lithium secondary battery - Google Patents
Electrolyte for lithium secondary batteryInfo
- Publication number
- JPH0744042B2 JPH0744042B2 JP63302945A JP30294588A JPH0744042B2 JP H0744042 B2 JPH0744042 B2 JP H0744042B2 JP 63302945 A JP63302945 A JP 63302945A JP 30294588 A JP30294588 A JP 30294588A JP H0744042 B2 JPH0744042 B2 JP H0744042B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- solvent
- charge
- secondary battery
- negative electrode
- 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 - Lifetime
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、リチウム二次電池の電解液に関するものであ
る。TECHNICAL FIELD The present invention relates to an electrolytic solution for a lithium secondary battery.
従来の技術 従来よりチリウム二次電池は正極活物質に二硫化モリブ
デン（MoS2）、二硫化チタン（TiS2）、二酸化マンガン
（MnO2）、五酸化バナジウム（V2O5）などの遷移金属硫
化物もしくは酸化物を用い、負極に金属リチウムやリチ
ウムイオンを吸蔵、放出する合金、たとえばウッド合金
やLi−Al合金などを用いた電池系が知られている。2. Description of the Related Art Conventionally, thirium secondary batteries have been used as positive electrode active materials for transition metals such as molybdenum disulfide (MoS 2 ), titanium disulfide (TiS 2 ), manganese dioxide (MnO 2 ), and vanadium pentoxide (V 2 O 5 ). A battery system using a sulfide or an oxide and an alloy that absorbs and releases metallic lithium or lithium ions in the negative electrode, such as a wood alloy or a Li-Al alloy, is known.
正極の充放電特性に関しては利用率が初期より低下し、
ある一定サイクル数から安定し、充放電効率（放電容量
／充電容量×100）も非常に高く、ほぼ100％に近い。Regarding the charge and discharge characteristics of the positive electrode, the utilization rate is lower than in the initial stage,
It is stable from a certain number of cycles, and the charging / discharging efficiency (discharging capacity / charging capacity × 100) is very high, close to 100%.
ところが負極に関しては、充放電効率が金属リチウムで
最高98％、リチウムイオンを吸蔵、放出する合金で99％
程度である。従ってリチウム二次電池のサイクル寿命を
支配しているのは負極であることがわかる。However, regarding the negative electrode, the charge / discharge efficiency is up to 98% for metallic lithium and 99% for alloys that absorb and release lithium ions.
It is a degree. Therefore, it is understood that the negative electrode controls the cycle life of the lithium secondary battery.
発明が解決しようとする課題 この正極と負極の充放電効率の差は、一般的に有機溶媒
が酸化、すなわち分子から電子を抜き取られる反応に強
く、逆に還元に弱いことから生じている。例えばプロピ
レンカーボネイト（PC）ではリチウムに対し、酸化分解
電位は5.0Vと正極の充電電位4Vに充分耐え得る程高い
が、還元分解電位は−40mVとリチウムに対し小さな分極
で分解してしまう。従って電池の充電の際、負極ではリ
チウムの析出反応と溶媒の分解反応の競合反応を起こす
ため負極の充放電効率は低くなる。特に負極にリチウム
金属を用いた場合はリチウムイオンを吸蔵、放出する合
金よりも充電電位が溶媒の還元分解電位に近いため、負
極の充放電効率が低い。Problems to be Solved by the Invention This difference in charge / discharge efficiency between the positive electrode and the negative electrode is generally caused by the fact that the organic solvent is strong in oxidation, that is, in a reaction of extracting an electron from a molecule, and conversely weak in reduction. For example, propylene carbonate (PC) has an oxidation decomposition potential of 5.0 V with respect to lithium, which is high enough to withstand a positive electrode charging potential of 4 V, but has a reduction decomposition potential of -40 mV and decomposes with a small polarization with respect to lithium. Therefore, when the battery is charged, the negative electrode causes a competitive reaction between the lithium precipitation reaction and the solvent decomposition reaction, so that the negative electrode charge / discharge efficiency becomes low. In particular, when lithium metal is used for the negative electrode, the charge potential is closer to the reductive decomposition potential of the solvent than the alloy that absorbs and releases lithium ions, so the charge and discharge efficiency of the negative electrode is low.
負極がリチウムイオンを吸蔵、放出する合金である場合
は、リチウムに対し電位が0.2〜0.6V貴であるため充放
電効率はリチウム金属よりも高くなるが、電池のエネル
ギー密度は逆に小さくなる。また容量密度はリチウム金
属の2062mAh/ccに対し、合金が1700mAh/ccと低いため、
内体積が限られている電池ではさらにエネルギー密度が
低下する。When the negative electrode is an alloy that absorbs and releases lithium ions, the charge / discharge efficiency is higher than that of lithium metal because the potential is 0.2 to 0.6 V noble with respect to lithium, but the energy density of the battery is conversely small. In addition, the capacity density of the alloy is as low as 1700 mAh / cc compared to 2062 mAh / cc of lithium metal,
Batteries with a limited internal volume have even lower energy densities.
従って高エネルギー密度のリチウム二次電池を実現させ
るためにはリチウム金属を負極とする方がよいと考えら
れる。しかしこの負極の充放電効率が約98％と低いた
め、たとえば、鉛蓄電池なみの300サイクルという電池
寿命を確保するためには正極の充放電容量に対しリチウ
ムはその約６倍という構成になり、エネルギー密度の観
点からすれば低くならざるを得ない状況である。Therefore, in order to realize a high energy density lithium secondary battery, it is considered better to use lithium metal as the negative electrode. However, since the charge and discharge efficiency of this negative electrode is as low as about 98%, for example, in order to ensure a battery life of 300 cycles like a lead storage battery, lithium is about 6 times as much as the charge and discharge capacity of the positive electrode. From the viewpoint of energy density, the situation is unavoidable.
このように従来の電池では高エネルギー密度で、かつ高
サイクル寿命を実現することは難しく、さらに耐還元性
の優れたリチウム二次電池用電解液が求められている。As described above, it is difficult to realize a high energy density and a long cycle life in a conventional battery, and there is a demand for an electrolytic solution for a lithium secondary battery having excellent reduction resistance.
本発明はこのような課題を解決することを目的とする。The present invention aims to solve such problems.
課題を解決するための手段 上記課題を解決するため、本発明はリチウム二次電池用
電解液に次式で示す鎖状炭酸エステル （但しR1≠R2、R1，R2は炭素数１〜４のアルキル基）を
単独もしくは他の溶媒との混合溶媒として用いたもので
ある。Means for Solving the Problems In order to solve the above problems, the present invention provides an electrolytic solution for a lithium secondary battery, which comprises a chain ester carbonate represented by the following formula: (However, R 1 ≠ R 2 , R 1 and R 2 are alkyl groups having 1 to 4 carbon atoms) are used alone or as a mixed solvent with another solvent.
作用 上記電解液を用いることにより、充電時に溶媒が還元さ
れ難く、そのため負極の充放電効率が向上し、従来の構
成より負極リチウム量も低減できるため、サイクル寿命
が長く、かつ高エネルギー密度のリチウム二次電池が得
られることとなる。By using the above-mentioned electrolytic solution, the solvent is less likely to be reduced at the time of charging, so that the charge / discharge efficiency of the negative electrode is improved, and the amount of negative electrode lithium can be reduced as compared with the conventional configuration, so that the cycle life is long and the lithium with high energy density is A secondary battery will be obtained.
実施例 以下、本発明の一実施例を第１図、第２図に基づき説明
する。Embodiment An embodiment of the present invention will be described below with reference to FIGS. 1 and 2.
第１図は本発明に係るリチウム二次電池の一部断面図で
あり、たとえば直径が20mm、高さが1.6mmのものであ
る。FIG. 1 is a partial cross-sectional view of a lithium secondary battery according to the present invention, which has a diameter of 20 mm and a height of 1.6 mm, for example.
第１図中、１は有機溶媒（以下、溶媒という）に電解質
として六フッ化リン酸リチウム（LiPF6）を１モル/l溶
解した電解液をしみこませたポリプロピレン製セパレー
タである。この溶媒の主溶媒として直鎖炭酸エステル （但しR1≠R2、R1，R2は炭素数１〜４のアルキル基） が使用される。２は負極活物質としてのリチウム金属で
あり、ステンレス製封口板３の内面に形成したステンレ
ス製負極集電体４に圧着固定されている。５は二酸化マ
ンガンを正極活物質とした正極合剤であり、ステンレス
製ケース６の内面に固定したチタン製正極集電体７に圧
着固定されている。８はポリプロピレン製ガスケットで
ある。なお、正極合剤５は、たとえば組成が重量部でMn
O2100に対し、カーボンブラック20、フッ素樹脂系結着
剤20とし、容量が10mAhとなるようにされている。リチ
ウム金属２は容量が25mAhとなるようにされている。In FIG. 1, reference numeral 1 denotes a polypropylene separator impregnated with an electrolytic solution obtained by dissolving lithium hexafluorophosphate (LiPF 6 ) as an electrolyte in an organic solvent (hereinafter referred to as a solvent) at 1 mol / l. Linear carbonate as the main solvent of this solvent (However, R 1 ≠ R 2 , R 1 and R 2 are alkyl groups having 1 to 4 carbon atoms) are used. Reference numeral 2 denotes lithium metal as a negative electrode active material, which is pressure-bonded and fixed to a stainless steel negative electrode current collector 4 formed on the inner surface of a stainless steel sealing plate 3. Reference numeral 5 denotes a positive electrode mixture containing manganese dioxide as a positive electrode active material, which is fixed by pressure to a titanium positive electrode current collector 7 fixed to the inner surface of a stainless case 6. 8 is a polypropylene gasket. The positive electrode mixture 5 has, for example, a composition of Mn in parts by weight.
With respect to O 2 100, carbon black 20 and fluororesin-based binder 20 were used, and the capacity was set to 10 mAh. Lithium metal 2 has a capacity of 25 mAh.
ここで、上記構成の電池において、溶媒を各種異ならせ
た場合のサイクル特性を調べた結果を第２図に示す。な
お、充電は0.5mAhの電流で3.8Vまで行い、放電は1.5mAh
の電流で2.0Vまで行った。また第２図中Ａ〜Ｇまでの溶
媒の成分を第１表に示す。混合溶媒の場合の組成比は体
積比で1:1であり、かつ電解質LiPF6の濃度は１モル/lで
ある。Here, FIG. 2 shows the results of examining the cycle characteristics of the battery having the above-mentioned structure when various solvents were used. In addition, charging is up to 3.8 V at a current of 0.5 mAh, discharging is 1.5 mAh
Current up to 2.0V. Table 1 shows the components of the solvents A to G in FIG. In the case of the mixed solvent, the composition ratio is 1: 1 by volume, and the concentration of the electrolyte LiPF 6 is 1 mol / l.
なお、比較のために、R1＝R2で炭素数１の炭酸ジメチル
（DMC）、炭素数２の炭酸ジエチル（DEC）、炭酸プロピ
レン（PC）、及び炭酸プロピレンとジメトキシエタン
（DME）との混合溶媒についても示した。 For comparison, R 1 = R 2 and dimethyl carbonate (DMC) having 1 carbon atom, diethyl carbonate (DEC) having 2 carbon atoms, propylene carbonate (PC), and propylene carbonate and dimethoxyethane (DME) Mixed solvents are also shown.
第２図より本発明の溶媒を使用した電池（図中B,C,D）
が他のものよりサイクル寿命が長いことがわかる。From FIG. 2, batteries using the solvent of the present invention (B, C, D in the figure)
Shows that the cycle life is longer than the others.
R1＝R2で炭素数１の炭酸ジメチルＡは構造的に対象性が
良く、融点が0.5℃と高く、実際にリチウム二次電池の
溶媒としては使い難い。また炭素数２の炭酸ジエチルＥ
は炭酸数が多いだけ構造的自由度が高く融点も低くなる
が、逆に誘電率が低くなり、電解質の溶解度は低くなる
ため溶媒としては使い難い。さらに炭酸プロピレンＦで
は融点も低く、誘電率も高いが、耐還元性に劣るためサ
イクル寿命が短くなっている。Dimethyl carbonate A having R 1 = R 2 and 1 carbon atom has structurally good symmetry and has a high melting point of 0.5 ° C., so that it is actually difficult to use as a solvent for a lithium secondary battery. Also, C2 diethyl carbonate E
The higher the carbon number, the higher the degree of structural freedom and the lower the melting point, but the lower the dielectric constant and the lower the solubility of the electrolyte, the more difficult it is to use as a solvent. Further, propylene carbonate F has a low melting point and a high dielectric constant, but its cycle life is short because of its poor resistance to reduction.
これらに対し、本発明の溶媒B,C,Dは炭酸ジメチル、炭
酸ジエチルと同等以上のサイクル寿命を示し、かつ構造
が非対称であるため、融点も低く、リチウム二次電池用
の溶媒としては非常に有用である。本発明で炭素数が４
より大となるアルキル基をもつと分子自体が嵩ばり、粘
性の増大、さらには誘電率の低下を引き起こし、リチウ
ム二次電池用の溶媒としては使い難くなる。On the other hand, the solvents B, C, and D of the present invention show a cycle life equivalent to or longer than that of dimethyl carbonate and diethyl carbonate, and have an asymmetric structure, so that they have a low melting point and are extremely useful as a solvent for a lithium secondary battery. Useful for. 4 carbon atoms in the present invention
If it has a larger alkyl group, the molecule itself becomes bulky, causing an increase in viscosity and a decrease in dielectric constant, making it difficult to use as a solvent for a lithium secondary battery.
第２図から得られたサイクル寿命から負極の充放電効率
を以下の式によって算出した結果、 は電池すなわち正極の平均充放電容量で、ここでは第
２図より9mAhである。Qexはリチウムの容量から充放電
中に正極に残存したリチウム容量を除いたもの、すなわ
ち充放電中に消費されたリチウム量を示し、ここでは20
mAh（リチウム量25mAh−サイクル寿命時の容量5mAh）と
なる。ｎはサイクル寿命で、ここでは50％の容量劣化時
のサイクル数をサイクル寿命とした。From the cycle life obtained from FIG. 2, the charge and discharge efficiency of the negative electrode was calculated by the following formula, Is the average charge / discharge capacity of the battery, that is, the positive electrode, which is 9 mAh from FIG. 2 here. Qex is the lithium capacity less the lithium capacity remaining in the positive electrode during charging / discharging, that is, the amount of lithium consumed during charging / discharging.
mAh (lithium amount 25 mAh-capacity at cycle life 5 mAh). n is the cycle life, and here, the number of cycles at 50% capacity deterioration is taken as the cycle life.
本発明の溶媒を用いた電池B,C,Dの負極の充放電効率は
第２表に示すように全て98.5〜99.0％を示し、従来の溶
媒A,E,F,Gを用いた電池よりも高いことがわかる。本実
施例に用いた電池は負極の充放電効率を時間的に早く算
出するためリチウム量Qex（20mAh）を正極に充放電容量
（9mAh）に対し、2.2倍にしているため、300サイクルま
でには至らない構成になっている。しかし第２表で算出
した充放電効率を用いることによって300サイクルの寿
命を達成できる電池にするためのリチウム量がわかり、
電池設計ができる。すなわち、負極の充放電効率が98.5
〜99.0％である本発明の溶媒を用いると、上記式から30
0サイクルの寿命を有する電池を設計するためのリチウ
ム量が算出でき、そのリチウム量Qexは第２表に示すよ
うに正極の充放電容量の3.0〜4.5倍となる。一方、従来
の溶媒A,E,F,Gを用いた電池では正極の充放電容量の5.7
〜18.9倍になる。従って、本発明と従来の溶媒を用いた
電池を比較するとわかるように従来のように負極の充放
電効率が低ければ低い程電池内にリチウム量が必要で、
逆に本発明のように負極の充放電効率が高い程、電池内
のリチウム量は少なくて良い。従って本発明の電池はリ
チウム量が少ない分だけ正極活物質の充填量を増すこと
ができ、これによって電池の高容量化すなわち高エネル
ギー密度化が可能となる。As shown in Table 2, the charge and discharge efficiencies of the negative electrodes of the batteries B, C and D using the solvent of the present invention were all 98.5 to 99.0%, and the battery using the conventional solvents A, E, F and G You can see that it is also expensive. In the battery used in this example, the lithium amount Qex (20 mAh) was set to 2.2 times the charge / discharge capacity (9 mAh) in the positive electrode in order to calculate the charging / discharging efficiency of the negative electrode quickly in time. Is not reached. However, by using the charge and discharge efficiency calculated in Table 2, the amount of lithium for a battery that can achieve a life of 300 cycles was found,
Can design batteries. That is, the charge / discharge efficiency of the negative electrode is 98.5.
With the solvent of the present invention, which is ~ 99.0%,
The amount of lithium for designing a battery having a life of 0 cycle can be calculated, and the amount of lithium Qex is 3.0 to 4.5 times the charge / discharge capacity of the positive electrode as shown in Table 2. On the other hand, in batteries using conventional solvents A, E, F, and G, the charge and discharge capacity of the positive electrode was 5.7%.
~ 18.9 times. Therefore, as can be seen by comparing the battery using the present invention and the conventional solvent, the lower the charge and discharge efficiency of the negative electrode as in the conventional case, the more lithium amount is required in the battery,
Conversely, the higher the charge / discharge efficiency of the negative electrode as in the present invention, the smaller the amount of lithium in the battery may be. Therefore, in the battery of the present invention, the filling amount of the positive electrode active material can be increased as much as the amount of lithium is smaller, which allows the battery to have higher capacity, that is, higher energy density.
また負極の充放電効率と溶媒の耐還元性とは密接な関係
にあり、耐還元性の高い溶媒を用いたほど充電の際、電
解液とリチウムとの反応により消費されるリチウム量が
少なく抑えられ、負極の充放電効率が高くなる。そし
て、耐還元性の高い溶媒は、従来から知られているよう
なエチレンカーボネイト、プロピレンカーボネイト、テ
トラヒドロフラン、1,2ジメトキシエタン、アセトニト
リル、ジメチルホルムアミドなどを他の溶媒とし、これ
らと適宜組み合わせて混合した状態であっても、負極の
充放電効率を高めて電池の充放電サイクル寿命特性を向
上させることができる。このことから同一リチウム量で
あると耐還元性が高い溶媒を用いた場合ほど負極の充放
電効率が高くなり、サイクル寿命が長くなる。従って本
発明の溶媒は耐還元性が高く、リチウム二次電池用電解
液に用いる溶媒として優れたものであると言える。Also, there is a close relationship between the charge and discharge efficiency of the negative electrode and the reduction resistance of the solvent, and the higher the reduction resistance of the solvent used, the smaller the amount of lithium consumed by the reaction between the electrolyte and lithium during charging. Therefore, the charge and discharge efficiency of the negative electrode is increased. Then, the solvent having high resistance to reduction is ethylene carbonate, propylene carbonate, tetrahydrofuran, 1,2 dimethoxyethane, acetonitrile, dimethylformamide, etc. which are conventionally known as other solvents, and they are appropriately combined and mixed. Even in the state, the charge / discharge efficiency of the negative electrode can be increased and the charge / discharge cycle life characteristics of the battery can be improved. From this, when the amount of lithium is the same, the charge and discharge efficiency of the negative electrode becomes higher and the cycle life becomes longer when a solvent having high reduction resistance is used. Therefore, it can be said that the solvent of the present invention has high reduction resistance and is an excellent solvent for use in the electrolytic solution for a lithium secondary battery.
発明の効果 以上の説明から明らかなように本発明の溶媒を用いれば
負極の充放電効率を向上させることができ、その結果高
エネルギー密度でかつサイクル寿命が長いという特徴を
有するリチウム二次電池が得られる。 EFFECTS OF THE INVENTION As is clear from the above description, the charge and discharge efficiency of the negative electrode can be improved by using the solvent of the present invention, and as a result, a lithium secondary battery having a feature of high energy density and long cycle life can be obtained. can get.
第１図は本発明の一実施例における二次電池の一部断面
図、第２図は同二次電池のサイクル特性を示す図であ
る。 １……セパレータ、２……リチウム金属、５…正極。FIG. 1 is a partial sectional view of a secondary battery according to an embodiment of the present invention, and FIG. 2 is a diagram showing cycle characteristics of the secondary battery. 1 ... Separator, 2 ... Lithium metal, 5 ... Positive electrode.
Claims (1)
ウム二次電池用電解液であって、前記溶媒が次式で示す
鎖状炭酸エステル （但しR1≠R2、R1，R2は炭素数１〜４のアルキル基） の単独もしくは他の溶媒との混合溶媒であることを特徴
とするリチウム二次電池用電解液。1. An electrolytic solution for a lithium secondary battery comprising a solvent in which a lithium salt is dissolved, wherein the solvent is a chain ester carbonate represented by the following formula: (Wherein R 1 ≠ R 2 , R 1 and R 2 are alkyl groups having 1 to 4 carbon atoms) alone or as a mixed solvent with another solvent, an electrolytic solution for a lithium secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63302945A JPH0744042B2 (en) | 1988-11-30 | 1988-11-30 | Electrolyte for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63302945A JPH0744042B2 (en) | 1988-11-30 | 1988-11-30 | Electrolyte for lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02148665A JPH02148665A (en) | 1990-06-07 |
| JPH0744042B2 true JPH0744042B2 (en) | 1995-05-15 |
Family
ID=17915032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63302945A Expired - Lifetime JPH0744042B2 (en) | 1988-11-30 | 1988-11-30 | Electrolyte for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0744042B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69127251T3 (en) * | 1990-10-25 | 2005-01-13 | Matsushita Electric Industrial Co., Ltd., Kadoma | Non-aqueous electrochemical secondary battery |
| US5521027A (en) * | 1990-10-25 | 1996-05-28 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous secondary electrochemical battery |
| US5484669A (en) * | 1991-12-27 | 1996-01-16 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary batteries |
| DE69309861T2 (en) * | 1992-11-18 | 1997-09-11 | Sony Corp | Carbonate compounds, non-aqueous electrolyte solutions and batteries containing non-aqueous electrolyte solutions |
| FR2702311B1 (en) * | 1993-03-02 | 1995-04-14 | Accumulateurs Fixes | Electrolyte for rechargeable lithium generator. |
| JP3341524B2 (en) * | 1995-04-04 | 2002-11-05 | 宇部興産株式会社 | Electrolyte for lithium secondary battery |
| JP3416016B2 (en) * | 1997-03-18 | 2003-06-16 | 富士通株式会社 | Ion conductor for lithium secondary battery and lithium secondary battery using the same |
| US5962720A (en) * | 1997-05-29 | 1999-10-05 | Wilson Greatbatch Ltd. | Method of synthesizing unsymmetric organic carbonates and preparing nonaqueous electrolytes for alkali ion electrochemical cells |
| EP1890357B1 (en) | 2005-06-10 | 2012-06-13 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte solution, nonaqueous electrolyte secondary battery and carbonate compound |
| JP5109288B2 (en) * | 2006-05-10 | 2012-12-26 | 三菱化学株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056663A (en) * | 1975-11-03 | 1977-11-01 | P. R. Mallory & Co. Inc. | Performance in an organic electrolyte |
-
1988
- 1988-11-30 JP JP63302945A patent/JPH0744042B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056663A (en) * | 1975-11-03 | 1977-11-01 | P. R. Mallory & Co. Inc. | Performance in an organic electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02148665A (en) | 1990-06-07 |
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