JPH11121012A - Nonaqueous electrolytic battery - Google Patents
Nonaqueous electrolytic batteryInfo
- Publication number
- JPH11121012A JPH11121012A JP9277666A JP27766697A JPH11121012A JP H11121012 A JPH11121012 A JP H11121012A JP 9277666 A JP9277666 A JP 9277666A JP 27766697 A JP27766697 A JP 27766697A JP H11121012 A JPH11121012 A JP H11121012A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- negative electrode
- electrolyte battery
- chelate
- polymer
- 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
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は非水電解質電池に関
するもので、さらに詳しく言えば、充放電サイクル寿命
特性、保存性能を改良した非水電解質電池に関するもの
である。The present invention relates to a non-aqueous electrolyte battery, and more particularly, to a non-aqueous electrolyte battery having improved charge / discharge cycle life characteristics and storage performance.
【０００２】[0002]
【従来の技術】近年、電子機器の高性能化、小型化に伴
って、その電源として使用される電池にも小型化、軽量
化、高容量化の要求が高まり、それに対応できる非水電
解質電池、特にリチウムイオン電池が急速に普及してい
る。2. Description of the Related Art In recent years, as the performance and size of electronic devices have been improved, the demand for smaller, lighter, and higher capacity batteries has been increasing. In particular, lithium ion batteries are rapidly spreading.
【０００３】リチウムイオン電池は、リチウムを吸蔵、
放出可能な活物質を主体として構成された正極と負極と
が隔離体を介して配されてなり、前記正極は、正極活物
質としてのＬｉＣｏＯ2 ，ＬｉＮｉＯ2 ，ＬｉＭｎ2 Ｏ
4 等に導電剤としてのカーボンブラックや黒鉛、バイン
ダーとしてのポリフッ化ビニリデンを混合した正極合剤
がアルミニウムなどからなる正極集電体上に被着されて
なり、負極は、負極活物質としてのコークスや黒鉛等に
バインダーとしてのポリフッ化ビニリデンを混合した負
極合剤が銅などからなる負極集電体上に被着されてな
り、隔離体は多孔性ポリエチレンフィルムのようなセパ
レータからなる。そして、前記正極、負極、隔離体には
ヘキサフルオロリン酸リチウムのようなリチウム塩をプ
ロピレンカーボネート、エチレンカーボネートのような
非プロトン性溶媒やポリエチレンオキシドのようなポリ
マーに溶解させた電解液が含浸されてなる。[0003] Lithium-ion batteries occlude lithium,
A positive electrode mainly composed of a releasable active material and a negative electrode are arranged via an isolator, and the positive electrode comprises LiCoO 2 , LiNiO 2 , and LiMn 2 O as positive electrode active materials.
A positive electrode mixture obtained by mixing carbon black or graphite as a conductive agent and polyvinylidene fluoride as a binder on 4 or the like is deposited on a positive electrode current collector made of aluminum or the like, and the negative electrode is coke as a negative electrode active material. A negative electrode mixture obtained by mixing polyvinylidene fluoride as a binder with graphite or graphite is applied on a negative electrode current collector made of copper or the like, and the separator is made of a separator such as a porous polyethylene film. Then, the positive electrode, the negative electrode, and the separator are impregnated with an electrolyte obtained by dissolving a lithium salt such as lithium hexafluorophosphate in an aprotic solvent such as propylene carbonate or ethylene carbonate or a polymer such as polyethylene oxide. It becomes.
【０００４】上記したリチウムイオン電池では、充放電
を反復させると、内部インピーダンスが増大して放電容
量が減少するという問題があり、この問題を解決するた
めの種々の提案がなされている。[0004] In the above-mentioned lithium ion battery, there is a problem that, when charging and discharging are repeated, the internal impedance increases and the discharge capacity decreases, and various proposals for solving this problem have been made.
【０００５】たとえば、内部インピーダンスが増大する
のは合剤と集電体との結着性が低下するのが原因である
とし、これを改良するものとして、特開平７−１８３０
２７号公報に記載されたような、正極合剤、負極合剤中
のバインダーとしてのポリフッ化ビニリデンに架橋を施
すという提案、特開平９−１２９２４０号に記載された
ような、前記バインダー中にイミド化合物を添加すると
いう提案、特開平９−１３９１９９号公報に記載された
ような、バインダーにポリフッ化エチレンを使用すると
いう提案がある。[0005] For example, it is assumed that the increase in internal impedance is due to a decrease in the binding property between the mixture and the current collector.
No. 27, a proposal to crosslink polyvinylidene fluoride as a binder in a positive electrode mixture and a negative electrode mixture, and an imide in the binder as described in JP-A-9-129240. There is a proposal to add a compound, and a proposal to use polyfluoroethylene as a binder as described in JP-A-9-139199.
【０００６】また、上記した以外の原因としては、正極
活物質としてＬｉＭｎ2 Ｏ4 を使用したものが顕著であ
ることから、放電の過程で溶出したマンガンイオンが内
部インピーダンスの増大に寄与するのではないかという
推察や、電解液中に不純物として微量に水分が存在する
ことから、ヘキサフルオロリン酸リチウムのようなリチ
ウム塩が前記水分によって分解され、それによって生成
するフッ素が溶媒であるプロピレンカーボネート、エチ
レンカーボネートを分解するのではないかという推察が
ある。As a cause other than the above, the one using LiMn 2 O 4 as the positive electrode active material is conspicuous, so that manganese ions eluted during the discharge process contribute to an increase in internal impedance. Presumption that there is not, because there is a trace amount of water as impurities in the electrolyte solution, lithium salt such as lithium hexafluorophosphate is decomposed by the water, the resulting fluorine is a solvent propylene carbonate, There is speculation that ethylene carbonate may be decomposed.
【０００７】[0007]
【発明が解決しようとする課題】ところが、上記した合
剤と集電体との結着性の改良によっても内部インピーダ
ンスの増大を抑制するには至らず、マンガンイオンの存
在や溶媒の分解が内部インピーダンスの増大に寄与する
と仮定してもそれを抑制する有効な手段は見出せていな
いのが現状であった。However, even with the improvement of the binding property between the mixture and the current collector, the increase in the internal impedance has not been suppressed, and the presence of manganese ions and the decomposition of the solvent have not been improved. At present, no effective means has been found to suppress the impedance even if it is assumed to contribute to an increase in impedance.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するた
め、請求項１記載の発明は、正極と負極とが隔離体を介
して配されてなる非水電解質電池において、正極、負
極、隔離体の少なくとも一つがキレート高分子を含有す
ることを特徴とするものであり、これにより、合剤と集
電体とをキレートによって強固に被着させ、溶出した金
属イオンや生成したフッ素をキレートによって吸着させ
ることができる。In order to solve the above-mentioned problems, the invention according to claim 1 is directed to a non-aqueous electrolyte battery in which a positive electrode and a negative electrode are arranged via an isolator. Characterized in that at least one of them contains a chelate polymer, whereby the mixture and the current collector are firmly adhered by the chelate, and the eluted metal ions and generated fluorine are absorbed by the chelate. Can be done.
【０００９】また、請求項２記載の発明は、請求項１記
載の非水電解質電池において、正極はアルミニウム、チ
タンまたはステンレスからなる正極集電体上に、該正極
集電体を構成する金属のイオンの選択吸着性が高いキレ
ート高分子を含有する正極活物質を主体とする合剤が被
着されていることを特徴とするものであり、これによ
り、前記金属イオンとの間でキレートを形成させること
ができる。According to a second aspect of the present invention, in the nonaqueous electrolyte battery according to the first aspect, the positive electrode is formed on a positive electrode current collector made of aluminum, titanium, or stainless steel, and the metal constituting the positive electrode current collector is formed on the positive electrode current collector. It is characterized in that a mixture mainly composed of a positive electrode active material containing a chelate polymer having high selective adsorption of ions is applied, thereby forming a chelate with the metal ions. Can be done.
【００１０】また、請求項３記載の発明は、請求項２記
載の非水電解質電池において、キレート高分子はイミノ
二酢酸形、イミノプロピオン酸形のキレート樹脂である
ことを特徴とするものであり、これにより、正極集電体
を構成する金属のイオンとの間でキレートを形成させる
ことができる。According to a third aspect of the present invention, in the nonaqueous electrolyte battery according to the second aspect, the chelate polymer is an iminodiacetic acid type or iminopropionic acid type chelate resin. Thus, a chelate can be formed between the positive electrode current collector and metal ions constituting the positive electrode current collector.
【００１１】また、請求項４記載の発明は、請求項１記
載の非水電解質電池において、負極はニッケル、鉄、銅
またはステンレスからなる負極集電体上に、該負極集電
体を構成する金属のイオンの選択吸着性が高いキレート
高分子を含有することを特徴とするものであり、これに
より、前記金属イオンとの間でキレートを形成させるこ
とができる。According to a fourth aspect of the present invention, in the nonaqueous electrolyte battery according to the first aspect, the negative electrode is formed on a negative electrode current collector made of nickel, iron, copper, or stainless steel. It is characterized by containing a chelate polymer having a high selective adsorption of metal ions, whereby a chelate can be formed with the metal ions.
【００１２】また、請求項５記載の発明は、請求項４記
載の非水電解質電池において、キレート高分子はイミノ
二酢酸形、イミノプロピオン酸形、アミノリン酸形、ア
ミドキシム形、ピコリルアミン形またはポリアミン形の
キレート樹脂であることを特徴とするものであり、これ
により、負極集電体を構成する金属のイオンとの間でキ
レートを形成させることができる。According to a fifth aspect of the present invention, in the non-aqueous electrolyte battery according to the fourth aspect, the chelating polymer is an iminodiacetic acid type, an iminopropionic acid type, an aminophosphoric acid type, an amidoxime type, a picolylamine type or a polyamine. It is characterized in that it is a chelate resin of a shape, and thereby, it is possible to form a chelate with a metal ion constituting the negative electrode current collector.
【００１３】また、請求項６記載の発明は、請求項１記
載の非水電解質電池において、隔離体は正極活物質を構
成する金属のイオンの選択吸着性が高いキレート高分子
を含有することを特徴とするものであり、これにより、
放電の過程で溶出した正極活物質を構成する金属イオン
をキレートによって吸着させることができる。According to a sixth aspect of the present invention, in the nonaqueous electrolyte battery according to the first aspect, the separator contains a chelate polymer having high selective adsorption of metal ions constituting the positive electrode active material. It is characterized by this,
Metal ions constituting the positive electrode active material eluted in the process of discharging can be adsorbed by the chelate.
【００１４】また、請求項７記載の発明は、請求項６記
載の非水電解質電池において、正極活物質を構成する金
属はマンガンを含むものであることを特徴とするもので
あり、これにより、マンガンイオンをキレートによって
吸着させることができる。According to a seventh aspect of the present invention, in the non-aqueous electrolyte battery according to the sixth aspect, the metal constituting the positive electrode active material contains manganese, whereby the manganese ion Can be adsorbed by chelating.
【００１５】また、請求項８記載の発明は、請求項６ま
たは７記載の非水電解質電池において、隔離体はイミノ
二酢酸形またはアミノリン酸形のキレート樹脂を含有し
たものであることを特徴とするものであり、これによ
り、放電の過程で溶出した正極活物質を構成する金属イ
オンをキレートによって吸着させることができる。The invention according to claim 8 is the non-aqueous electrolyte battery according to claim 6 or 7, wherein the separator contains an iminodiacetic acid type or aminophosphate type chelate resin. Thereby, the metal ions constituting the positive electrode active material eluted in the process of discharging can be adsorbed by the chelate.
【００１６】[0016]
【発明の実施の形態】以下、本発明をその実施の形態に
基づいて説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on its embodiments.
【００１７】図１は本発明の実施の形態に係る非水電解
質電池の断面図である。FIG. 1 is a sectional view of a nonaqueous electrolyte battery according to an embodiment of the present invention.
【００１８】図１において、正極１０は、正極合剤１を
正極集電体６上に被着してなるもので、前記正極合剤１
は、正極活物質としての平均粒径が１０μｍのＬｉＣｏ
Ｏ2（８３重量部）、導電剤としての黒鉛粉末（１０重
量部）、キレート高分子としてのイミノ二酢酸形のキレ
ート樹脂（４重量部）、バインダーとしてのポリフッ化
ビニリデン（３重量部）からなり、この正極合剤１を、
プロピレンカーボネートとジエチルカーボネートとの混
合溶媒に溶質としてのヘキサフルオロリン酸リチウムを
溶解させた電解液に混合してスラリー状にし、厚さが約
２０μｍのアルミニウムからなる正極集電体６上に塗布
して約１００μｍの厚さにする。In FIG. 1, a positive electrode 10 is obtained by applying a positive electrode mixture 1 on a positive electrode current collector 6.
Is LiCo having an average particle size of 10 μm as a positive electrode active material.
O 2 (83 parts by weight), graphite powder (10 parts by weight) as a conductive agent, iminodiacetic acid type chelate resin (4 parts by weight) as a chelating polymer, and polyvinylidene fluoride (3 parts by weight) as a binder This positive electrode mixture 1
It is mixed with an electrolyte solution in which lithium hexafluorophosphate as a solute is dissolved in a mixed solvent of propylene carbonate and diethyl carbonate to form a slurry, and is coated on a positive electrode current collector 6 made of aluminum having a thickness of about 20 μm. To a thickness of about 100 μm.
【００１９】前記正極１０の、正極合剤１は正極活物質
としてのＬｉＣｏＯ2 以外に、ＬｉＮｉＯ2 ，ＬｉＭｎ
2 Ｏ4 ，ＬｉＭｎＯ2 などのリチウム遷移金属酸化物、
Ｖ2Ｏ5 ，ＭｎＯ2 ，ＭｏＯ3 などの遷移金属酸化物、
ＴｉＳ2 ，ＭｏＳ2 ，ＮｂＳｅ3 などのカルコゲン化合
物やこれらを併用したものが使用でき、キレート高分子
としてのイミノ二酢酸形のキレート樹脂以外に、イミノ
プロピオン酸形のキレート樹脂が使用でき、正極集電体
６はアルミニウム以外に、チタン、ステンレスが使用で
きる。The positive electrode mixture 1 of the positive electrode 10 includes LiNiO 2 , LiMn, in addition to LiCoO 2 as a positive electrode active material.
Lithium transition metal oxides such as 2 O 4 and LiMnO 2 ,
Transition metal oxides such as V 2 O 5 , MnO 2 and MoO 3 ;
Chalcogen compounds such as TiS 2 , MoS 2 , NbSe 3 and the like can be used, and in addition to an iminodiacetate type chelate resin as a chelate polymer, an iminopropionic acid type chelate resin can be used. As the electric body 6, titanium or stainless steel can be used in addition to aluminum.
【００２０】すなわち、前記キレート高分子は正極集電
体６を構成する金属のイオンの選択吸着性が高いもので
あればよく、その正極合剤１中の含有率は１〜１０重量
％が好ましい。なお、含有率が１重量％以下であると、
正極合剤１と正極集電体６とが強固に接着されなくな
り、含有率が１０重量％以上であると、正極合剤１の電
気抵抗が増大して実用に適さなくなる。In other words, the chelate polymer only needs to have a high selective adsorption of metal ions constituting the positive electrode current collector 6, and its content in the positive electrode mixture 1 is preferably 1 to 10% by weight. . When the content is 1% by weight or less,
When the positive electrode mixture 1 and the positive electrode current collector 6 are not firmly adhered to each other, and when the content is 10% by weight or more, the electric resistance of the positive electrode mixture 1 increases, which is not suitable for practical use.
【００２１】なお、正極合剤１と正極集電体６との間に
プライマー層を介在させた場合には、このプライマー層
にキレート高分子を含有させてもよい。When a primer layer is interposed between the positive electrode mixture 1 and the positive electrode current collector 6, the primer layer may contain a chelate polymer.
【００２２】次に、負極２０は、負極合剤２を負極集電
体７上に被着してなるもので、前記負極合剤２は、負極
活物質としての平均粒径が１０μｍの黒鉛（９３重量
部）、キレート高分子としてのイミノ二酢酸形のキレー
ト樹脂（４重量部）、バインダーとしてのポリフッ化ビ
ニリデン（３重量部）からなり、この負極合剤２を、プ
ロピレンカーボネートとジエチルカーボネートとの混合
溶媒に溶質としてのヘキサフルオロリン酸リチウムを溶
解させた電解液に混合してスラリー状にし、厚さが約２
０μｍの銅からなる負極集電体７上に塗布して約１００
μｍの厚さにする。Next, the negative electrode 20 is obtained by depositing the negative electrode mixture 2 on the negative electrode current collector 7. The negative electrode mixture 2 is made of graphite having an average particle diameter of 10 μm as a negative electrode active material. 93 parts by weight), an iminodiacetic acid-type chelate resin (4 parts by weight) as a chelate polymer, and polyvinylidene fluoride (3 parts by weight) as a binder. This negative electrode mixture 2 was prepared by mixing propylene carbonate and diethyl carbonate. And mixed with an electrolyte in which lithium hexafluorophosphate as a solute is dissolved in a mixed solvent of
About 100 μm on a negative electrode current collector 7 made of copper
Make a thickness of μm.
【００２３】前記負極２０の、負極合剤２は負極活物質
としての黒鉛以外に、リチウム−アルミニウム合金、リ
チウム−珪素合金、リチウム−インジウム合金などのリ
チウム合金、コークス、有機物焼成体などの炭素材料や
これらを併用したものが使用でき、キレート高分子とし
てのイミノ二酢酸形のキレート樹脂以外に、イミノプロ
ピオン酸形、アミノリン酸形、アミドキシム形、ピコリ
ルアミン形、ポリアミン形のキレート樹脂が使用でき、
負極集電体７は銅以外に、ニッケル、鉄、ステンレスが
使用できる。The negative electrode mixture 2 of the negative electrode 20 is made of a carbon material such as a lithium-aluminum alloy, a lithium-silicon alloy, a lithium-indium alloy or the like, a coke, or a fired organic material in addition to graphite as a negative electrode active material. And a combination thereof can be used.In addition to an iminodiacetic acid type chelating resin as a chelating polymer, an iminopropionic acid type, an aminophosphoric acid type, an amidoxime type, a picolylamine type, and a polyamine type chelating resin can be used.
Nickel, iron, and stainless steel can be used for the negative electrode current collector 7 in addition to copper.
【００２４】すなわち、前記キレート高分子は負極集電
体７を構成する金属のイオンの選択吸着性が高いもので
あればよく、その負極合剤２中の含有率は１〜１０重量
％が好ましい。なお、含有率が１重量％以下であると、
負極合剤２と負極集電体７とが強固に接着されなくな
り、含有率が１０重量％以上であると、負極合剤２の電
気抵抗が増大して実用に適さなくなる。In other words, the chelate polymer only needs to have high selective adsorption of ions of the metal constituting the negative electrode current collector 7, and its content in the negative electrode mixture 2 is preferably 1 to 10% by weight. . When the content is 1% by weight or less,
When the negative electrode mixture 2 and the negative electrode current collector 7 are not firmly bonded to each other, and the content is 10% by weight or more, the electric resistance of the negative electrode mixture 2 increases, and the negative electrode mixture 2 becomes unsuitable for practical use.
【００２５】なお、負極合剤２と負極集電体７との間に
プライマー層を介在させた場合には、このプライマー層
にキレート高分子を含有させてもよい。When a primer layer is interposed between the negative electrode mixture 2 and the negative electrode current collector 7, the primer layer may contain a chelate polymer.
【００２６】次に、前記正極１０または負極２０にキレ
ート高分子を含有させた場合は、キレート高分子を含有
しないポリエチレン、ポリプロピレンなどの微多孔性フ
ィルムからなるセパレータを隔離体３として使用しても
よいが、正極１０または負極２０にキレート高分子を含
有させた場合であっても、前述した正極活物質を構成す
る金属のイオンの選択吸着性が高いキレート高分子を含
有したものを隔離体３として使用してもよい。Next, when the positive electrode 10 or the negative electrode 20 contains a chelate polymer, a separator made of a microporous film such as polyethylene or polypropylene containing no chelate polymer can be used as the separator 3. However, even if the positive electrode 10 or the negative electrode 20 contains a chelate polymer, the separator 3 containing the chelate polymer having high selective adsorption of metal ions constituting the positive electrode active material is used. You may use as.
【００２７】すなわち、隔離体３自体を、適度に架橋さ
れた微多孔性のキレート樹脂としたり、隔離体３を、セ
パレータとしてのポリエチレン、ポリプロピレンなどの
微多孔性フィルムをキレート高分子としてのキレート樹
脂フィルムの少なくとも一方の面に配した積層体とした
り、隔離体３を、ヘキサフルオロリン酸リチウムのよう
なリチウム塩を架橋性のポリエチレンオキシドなどのポ
リマーに溶解した高分子固体電解質中またはヘキサフル
オロリン酸リチウムをプロピレンカーボネート、エチレ
ンカーボネート、エチルメチルカーボネートまたはジエ
チルカーボネートなどの溶媒とポリアクリロニトリルま
たはポリメチルメタアクリレートなどの高分子ゲルとの
混合物に溶解した高分子ゲル電解質中に、キレート高分
子としてのキレート樹脂を分散させたものとすることが
できる。That is, the separator 3 itself may be a moderately crosslinked microporous chelate resin, or the separator 3 may be a microporous film such as polyethylene or polypropylene as a separator and a chelate resin as a chelate polymer. A laminate may be formed on at least one surface of the film, or the separator 3 may be formed in a polymer solid electrolyte in which a lithium salt such as lithium hexafluorophosphate is dissolved in a polymer such as crosslinkable polyethylene oxide or hexafluorophosphate. Chelate as a chelate polymer in a polymer gel electrolyte in which lithium oxide is dissolved in a mixture of a solvent such as propylene carbonate, ethylene carbonate, ethyl methyl carbonate or diethyl carbonate and a polymer gel such as polyacrylonitrile or polymethyl methacrylate It can be assumed that the resin is dispersed.
【００２８】前述したポリエチレン、ポリプロピレンな
どの微多孔性フィルムを、キレート樹脂フィルムの少な
くとも一方の面に配した積層体とすることにより、キレ
ート樹脂フィルムが正極１０、負極２０に直接接触する
のを防止することができ、キレート樹脂フィルムが酸
化、還元されて劣化するのを防止することができる。By forming the above-mentioned microporous film of polyethylene, polypropylene or the like on a laminate in which at least one surface of the chelate resin film is disposed, it is possible to prevent the chelate resin film from directly contacting the positive electrode 10 and the negative electrode 20. It is possible to prevent the chelate resin film from being oxidized and reduced and deteriorated.
【００２９】上記したキレート高分子を含有した隔離体
は、正極活物質を構成する金属のイオンがマンガンイオ
ンである場合に特に有効である。The separator containing the above chelate polymer is particularly effective when the metal ion constituting the positive electrode active material is manganese ion.
【００３０】すなわち、正極活物質がＬｉＭｎ2 Ｏ4 ，
ＬｉＭｎＯ2 のようなマンガンの酸化物の場合には、電
解液中に溶出したマンガンイオンが隔離体３に含有され
るキレート高分子によって捕捉されるため、保存中に自
己放電が抑制できる効果もある。That is, when the positive electrode active material is LiMn 2 O 4 ,
In the case of a manganese oxide such as LiMnO 2 , since manganese ions eluted in the electrolytic solution are captured by the chelate polymer contained in the separator 3, there is also an effect that self-discharge can be suppressed during storage. .
【００３１】上記した正極１０、負極２０、隔離体３に
含有させるキレート高分子としては水素やナトリウムが
リチウムと置換されたリチウム置換形のものがよい。As the chelate polymer contained in the positive electrode 10, the negative electrode 20, and the separator 3, a lithium-substituted type in which hydrogen or sodium is substituted with lithium is preferable.
【００３２】なお、図１において、４は正極端子を兼ね
る正極容器、５は負極端子を兼ねる負極容器、８は正極
容器４と負極容器５との間を絶縁するガスケットであ
る。In FIG. 1, reference numeral 4 denotes a positive electrode container also serving as a positive electrode terminal, 5 denotes a negative electrode container also serving as a negative electrode terminal, and 8 denotes a gasket for insulating between the positive electrode container 4 and the negative electrode container 5.
【００３３】[0033]
（実施例１） （評価試験１）８３重量％のＬｉＣｏＯ2 を正極活物質
として用い、３重量％のポリスチレンをベースとするリ
チウム置換形のイミノ二酢酸形のキレート樹脂をキレー
ト高分子として用いた正極合剤１を、アルミニウムから
なる正極集電体６に被着した正極１０と、９３重量％の
人造黒鉛を負極活物質として用い、３重量％のポリスチ
レンをベースとするリチウム置換形のアミノリン酸形の
キレート樹脂をキレート高分子として用いた負極合剤２
を、銅からなる負極集電体７に被着した負極２０と、隔
離体３としての厚さが２５μｍのポリエチレンの微多孔
性フィルムからなるセパレータとを用いて作製した本発
明に係る非水電解質電池（イ）、および正極合剤１およ
び負極合剤２中にキレート高分子を含有させない従来の
非水電解質電池（ロ）について、充電電流を０．５Ｃの
定電流、充電終止電圧を４．２Ｖとし、放電電流を０．
５Ｃの定電流、放電終止電圧を４．２Ｖとして充放電サ
イクル寿命試験を行い、結果を図２に示す。Example 1 (Evaluation Test 1) 83% by weight of LiCoO 2 was used as a positive electrode active material, and 3% by weight of a polystyrene-based lithium-substituted iminodiacetic acid-type chelate resin was used as a chelate polymer. The positive electrode mixture 1 is coated on a positive electrode current collector 6 made of aluminum, and a lithium-substituted aminophosphoric acid based on 3% by weight of polystyrene based on 93% by weight of artificial graphite as a negative electrode active material. Negative electrode mixture using a chelating resin in the form of a solid as a chelating polymer 2
Non-aqueous electrolyte according to the present invention prepared using a negative electrode 20 adhered to a negative electrode current collector 7 made of copper and a separator made of a microporous polyethylene film having a thickness of 25 μm as a separator 3 Regarding the battery (a) and the conventional nonaqueous electrolyte battery (b) in which the chelate polymer is not contained in the positive electrode mixture 1 and the negative electrode mixture 2, the charging current is 0.5 C and the charging end voltage is 4. 2V, and the discharge current was set at 0.
A charge / discharge cycle life test was performed at a constant current of 5 C and a discharge end voltage of 4.2 V, and the results are shown in FIG.
【００３４】図２から、本発明に係る非水電解質電池
（イ）は従来の非水電解質電池（ロ）より充放電サイク
ル寿命が良好であることがわかる。これは、本発明に係
る非水電解質電池（イ）では正極合剤１と正極集電体６
および負極合剤２と負極集電体７とが強固に接着できた
ためであると考えられる。FIG. 2 shows that the nonaqueous electrolyte battery (a) according to the present invention has a better charge / discharge cycle life than the conventional nonaqueous electrolyte battery (b). This is because in the nonaqueous electrolyte battery (a) according to the present invention, the positive electrode mixture 1 and the positive electrode current collector 6
This is considered to be because the negative electrode mixture 2 and the negative electrode current collector 7 could be firmly bonded.
【００３５】（評価試験２）上記した本発明に係る非水
電解質電池（イ）と従来の非水電解質電池（ロ）とを常
温下で１か月間放置し、その後の容量の低下率を調査し
たところ、本発明に係る非水電解質電池（イ）では４％
であったのに対し、従来の非水電解質電池（ロ）では１
３％であった。これは、本発明に係る非水電解質電池
（イ）では正極合剤１と正極集電体６との接着および負
極合剤２と負極集電体７との接着がほとんど変化しなか
ったためであると考えられる。(Evaluation Test 2) The above-described nonaqueous electrolyte battery (a) according to the present invention and the conventional nonaqueous electrolyte battery (b) were allowed to stand at room temperature for one month, and the rate of decrease in capacity thereafter was investigated. As a result, in the nonaqueous electrolyte battery (a) according to the present invention, 4%
In contrast, the conventional nonaqueous electrolyte battery (b)
3%. This is because in the nonaqueous electrolyte battery (a) according to the present invention, the adhesion between the positive electrode mixture 1 and the positive electrode current collector 6 and the adhesion between the negative electrode mixture 2 and the negative electrode current collector 7 hardly changed. it is conceivable that.
【００３６】（実施例２） （評価試験１）８３重量％のＬｉＭｎ2 Ｏ4 を正極活物
質として用い、３重量％のポリスチレンをベースとする
リチウム置換形のイミノ二酢酸形のキレート樹脂をキレ
ート高分子として用いた正極合剤１を、アルミニウムか
らなる正極集電体６に被着した正極１０と、９３重量％
の人造黒鉛を負極活物質として用い、３重量％のポリス
チレンをベースとするリチウム置換形のイミノ二酢酸形
のキレート樹脂をキレート高分子として用いた負極合剤
２を、銅からなる負極集電体７に被着した負極２０と、
隔離体３としての、厚さが５０μｍのポリスチレンをベ
ースとするリチウム置換形のアミノリン酸形のキレート
樹脂フィルムの両面に厚さが２５μｍのポリエチレンの
微多孔性フィルムからなるセパレータを配したものと用
いて作製した本発明に係る非水電解質電池（ハ）、およ
び正極合剤１および負極合剤２中にのみキレート高分子
を含有させ、隔離体３にキレート高分子を含有させない
本発明に係る非水電解質電池（ニ）、正極合剤１、負極
合剤２、隔離体３のいずれにもキレート高分子を含有さ
せない従来の非水電解質電池（ホ）について、充電電流
を０．５Ｃの定電流、充電終止電圧を４．２Ｖとし、放
電電流を０．５Ｃの定電流、放電終止電圧を４．２Ｖと
して充放電サイクル寿命試験を行い、結果を図３に示
す。Example 2 (Evaluation Test 1) A lithium-substituted iminodiacetate type chelate resin based on 3% by weight of polystyrene was chelated using 83% by weight of LiMn 2 O 4 as a positive electrode active material. The positive electrode mixture 1 used as a polymer was mixed with a positive electrode 10 coated on a positive electrode current collector 6 made of aluminum and 93% by weight.
A negative electrode current collector made of copper, using an artificial graphite as a negative electrode active material and a negative electrode mixture 2 using a lithium-substituted iminodiacetic acid type chelate resin based on 3% by weight of polystyrene as a chelate polymer. 7, a negative electrode 20 attached to
The separator 3 is a 50 μm thick polystyrene-based chelating resin film of a lithium-substituted aminophosphoric acid type based on polystyrene and a separator made of a 25 μm thick polyethylene microporous film on both sides. And the nonaqueous electrolyte battery (c) according to the present invention, and the nonaqueous electrolyte battery according to the present invention in which the chelate polymer is contained only in the positive electrode mixture 1 and the negative electrode mixture 2 and the separator 3 does not contain the chelate polymer. A non-aqueous electrolyte battery (e) in which the chelating polymer is not contained in any of the water electrolyte battery (d), the positive electrode mixture 1, the negative electrode mixture 2, and the separator 3 has a charging current of 0.5 C. A charge-discharge cycle life test was performed with the charge end voltage set to 4.2 V, the discharge current set to a constant current of 0.5 C, and the discharge end voltage set to 4.2 V. The results are shown in FIG.
【００３７】図３から、本発明に係る非水電解質電池
（ハ），（ニ）は従来の非水電解質電池（ホ）より充放
電サイクル寿命が良好であることがわかる。これは、本
発明に係る非水電解質電池（ハ），（ニ）では正極合剤
１と正極集電体６および負極合剤２と負極集電体７とが
強固に接着できたためであると考えられる。FIG. 3 shows that the nonaqueous electrolyte batteries (c) and (d) according to the present invention have better charge / discharge cycle life than the conventional nonaqueous electrolyte battery (e). This is because in the nonaqueous electrolyte batteries (c) and (d) according to the present invention, the positive electrode mixture 1 and the positive electrode current collector 6 and the negative electrode mixture 2 and the negative electrode current collector 7 could be firmly bonded. Conceivable.
【００３８】（評価試験２）上記した本発明に係る非水
電解質電池（ハ），（ニ）と従来の非水電解質電池
（ホ）とを常温下で１か月間放置し、その後の容量の低
下率を調査したところ、本発明に係る非水電解質電池
（ハ）では６％、本発明に係る非水電解質電池（ニ）で
は１１％であったのに対し、従来の非水電解質電池
（ホ）では１８％であった。これは、本発明に係る非水
電解質電池（ハ）では正極合剤１と正極集電体６との接
着および負極合剤２と負極集電体７との接着がほとんど
変化しなかっただけでなく、本発明に係る非水電解質電
池（ニ）に対して溶出したマンガンイオンが隔離体３に
よって捕捉できたためであるとと考えられる。(Evaluation Test 2) The non-aqueous electrolyte batteries (c) and (d) according to the present invention and the conventional non-aqueous electrolyte battery (e) were allowed to stand at room temperature for one month, and the remaining capacity was reduced. When the rate of decrease was investigated, it was 6% for the nonaqueous electrolyte battery (c) according to the present invention and 11% for the nonaqueous electrolyte battery (d) according to the present invention. E) was 18%. This is because in the nonaqueous electrolyte battery (C) according to the present invention, the adhesion between the positive electrode mixture 1 and the positive electrode current collector 6 and the adhesion between the negative electrode mixture 2 and the negative electrode current collector 7 hardly changed. It is considered that manganese ions eluted with respect to the nonaqueous electrolyte battery (d) according to the present invention could be captured by the separator 3.
【００３９】[0039]
【発明の効果】上記した如く、各請求項記載の発明は、
正極、負極、隔離体の少なくとも一つにキレート高分子
を含有させたことによって充放電サイクル寿命特性、保
存性能を改良することができ、非水電解質電池の高性能
化に寄与するところが大であり、特に正極活物質がＬｉ
Ｍｎ2 Ｏ4 のようなマンガン酸化物である場合には、そ
の保存性能の向上に寄与するところが大である。As described above, the invention described in each claim is
By including a chelate polymer in at least one of the positive electrode, the negative electrode, and the separator, the charge-discharge cycle life characteristics and storage performance can be improved, which greatly contributes to the high performance of nonaqueous electrolyte batteries. Especially when the positive electrode active material is Li
When it is a manganese oxide such as Mn 2 O 4 , it greatly contributes to the improvement of its storage performance.
【図１】本発明の実施の形態に係る非水電解質電池の断
面図である。FIG. 1 is a cross-sectional view of a nonaqueous electrolyte battery according to an embodiment of the present invention.
【図２】本発明の実施例１に対する評価試験１の結果を
示した図である。FIG. 2 is a diagram showing the results of evaluation test 1 for Example 1 of the present invention.
【図３】本発明の実施例２に対する評価試験１の結果を
示した図である。FIG. 3 is a diagram showing the results of an evaluation test 1 for Example 2 of the present invention.
１ 正極合剤 ２ 負極合剤 ３ 隔離体 ６ 正極集電体 ７ 負極集電体 １０ 正極 ２０ 負極 DESCRIPTION OF SYMBOLS 1 Positive electrode mixture 2 Negative electrode mixture 3 Separator 6 Positive electrode collector 7 Negative electrode collector 10 Positive electrode 20 Negative electrode
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｍ 4/50 Ｈ０１Ｍ 4/50 10/40 10/40 Ｂ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI H01M 4/50 H01M 4/50 10/40 10/40 B
Claims (8)
なる非水電解質電池において、正極、負極、隔離体の少
なくとも一つがキレート高分子を含有することを特徴と
する非水電解質電池。1. A non-aqueous electrolyte battery in which a positive electrode and a negative electrode are arranged via an isolator, wherein at least one of the positive electrode, the negative electrode, and the isolator contains a chelate polymer. .
て、正極はアルミニウム、チタンまたはステンレスから
なる正極集電体上に、該正極集電体を構成する金属のイ
オンの選択吸着性が高いキレート高分子を含有する正極
活物質を主体とする合剤が被着されていることを特徴と
する電池。2. The non-aqueous electrolyte battery according to claim 1, wherein the positive electrode is a chelate having high selective adsorption of ions of a metal constituting the positive electrode current collector on a positive electrode current collector made of aluminum, titanium or stainless steel. A battery comprising a mixture mainly composed of a positive electrode active material containing a polymer.
て、キレート高分子はイミノ二酢酸形、イミノプロピオ
ン酸形のキレート樹脂であることを特徴とする非水電解
質電池。3. The non-aqueous electrolyte battery according to claim 2, wherein the chelating polymer is an iminodiacetic acid-type or iminopropionic acid-type chelating resin.
て、負極はニッケル、鉄、銅またはステンレスからなる
負極集電体上に、該負極集電体を構成する金属のイオン
の選択吸着性が高いキレート高分子を含有することを特
徴とする非水電解質電池。4. The non-aqueous electrolyte battery according to claim 1, wherein the negative electrode has a selective adsorption property of ions of a metal constituting the negative electrode current collector on a negative electrode current collector made of nickel, iron, copper, or stainless steel. A non-aqueous electrolyte battery comprising a high chelate polymer.
て、キレート高分子はイミノ二酢酸形、イミノプロピオ
ン酸形、アミノリン酸形、アミドキシム形、ピコリルア
ミン形またはポリアミン形のキレート樹脂であることを
特徴とする非水電解質電池。5. The non-aqueous electrolyte battery according to claim 4, wherein the chelating polymer is a chelating resin in the form of iminodiacetic acid, iminopropionic acid, aminophosphoric acid, amidoxime, picolylamine or polyamine. Characteristic non-aqueous electrolyte battery.
て、隔離体は正極活物質を構成する金属のイオンの選択
吸着性が高いキレート高分子を含有することを特徴とす
る非水電解質電池。6. The non-aqueous electrolyte battery according to claim 1, wherein the separator contains a chelate polymer having high selective adsorption of metal ions constituting the positive electrode active material.
て、正極活物質を構成する金属はマンガンを含むもので
あることを特徴とする非水電解質電池。7. The non-aqueous electrolyte battery according to claim 6, wherein the metal constituting the positive electrode active material contains manganese.
において、隔離体はイミノ二酢酸形またはアミノリン酸
形のキレート樹脂を含有したものであることを特徴とす
る非水電解質電池。8. The non-aqueous electrolyte battery according to claim 6, wherein the separator contains a chelating resin of an iminodiacetic acid type or an aminophosphoric acid type.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9277666A JPH11121012A (en) | 1997-10-09 | 1997-10-09 | Nonaqueous electrolytic battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9277666A JPH11121012A (en) | 1997-10-09 | 1997-10-09 | Nonaqueous electrolytic battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11121012A true JPH11121012A (en) | 1999-04-30 |
Family
ID=17586614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9277666A Pending JPH11121012A (en) | 1997-10-09 | 1997-10-09 | Nonaqueous electrolytic battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11121012A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000195553A (en) * | 1998-10-19 | 2000-07-14 | Shin Kobe Electric Mach Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2001243978A (en) * | 2000-02-28 | 2001-09-07 | Toyota Central Res & Dev Lab Inc | Lithium secondary battery |
| JP2007207690A (en) * | 2006-02-06 | 2007-08-16 | Asahi Kasei Chemicals Corp | Lithium-ion secondary battery |
| WO2009035132A1 (en) | 2007-09-13 | 2009-03-19 | Nitto Denko Corporation | Battery separator and nonaqueous lithium ion secondary battery having the same |
| JP2009123687A (en) * | 2007-10-26 | 2009-06-04 | Nitto Denko Corp | Separator for battery, and nonaqueous lithium-ion secondary battery |
| WO2012011555A1 (en) * | 2010-07-23 | 2012-01-26 | 日本ゼオン株式会社 | Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery |
| CN102422466A (en) * | 2009-05-11 | 2012-04-18 | 奈克松有限公司 | Binder for lithium ion rechargeable battery cells |
| JP2012089411A (en) * | 2010-10-21 | 2012-05-10 | Nippon Zeon Co Ltd | Cathode composition for lithium-ion secondary battery, cathode for lithium-ion secondary battery, and lithium-ion secondary battery |
| WO2012095805A1 (en) * | 2011-01-11 | 2012-07-19 | Etv Energy Ltd. | Membranes suitable for use as separators and electrochemical cells including such separators |
| CN102668171A (en) * | 2009-11-19 | 2012-09-12 | 吉列公司 | Alkaline battery separators with ion-trapping molecules |
| US20130149588A1 (en) * | 2011-12-07 | 2013-06-13 | Arnd Garsuch | Electrochemical cells comprising chelate ligands |
| JP2015002167A (en) * | 2013-06-14 | 2015-01-05 | 上海緑孚新能源科技有限公司Ｇｒｅｅｎｆｕｌ Ｎｅｗ Ｅｎｅｒｇｙ Ｃｏ．，Ｌｔｄ． | Secondary battery |
| JP2015524601A (en) * | 2013-01-28 | 2015-08-24 | エルジー・ケム・リミテッド | Lithium secondary battery |
| CN105474339A (en) * | 2013-08-22 | 2016-04-06 | 康宁股份有限公司 | Separator based on fibrous ceramic material for ultracapacitors, EDLC, hybrid capacitor, fuel cell and battery |
| US9882239B2 (en) | 2013-01-28 | 2018-01-30 | Lg Chem, Ltd. | Composition for gel polymer electrolyte and lithium secondary battery including the same |
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-
1997
- 1997-10-09 JP JP9277666A patent/JPH11121012A/en active Pending
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000195553A (en) * | 1998-10-19 | 2000-07-14 | Shin Kobe Electric Mach Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2001243978A (en) * | 2000-02-28 | 2001-09-07 | Toyota Central Res & Dev Lab Inc | Lithium secondary battery |
| JP2007207690A (en) * | 2006-02-06 | 2007-08-16 | Asahi Kasei Chemicals Corp | Lithium-ion secondary battery |
| WO2009035132A1 (en) | 2007-09-13 | 2009-03-19 | Nitto Denko Corporation | Battery separator and nonaqueous lithium ion secondary battery having the same |
| JP2009087929A (en) * | 2007-09-13 | 2009-04-23 | Nitto Denko Corp | Battery separator and nonaqueous lithium-ion secondary battery using the same |
| US8349031B2 (en) | 2007-09-13 | 2013-01-08 | Nitto Denko Corporation | Battery separator and nonaqueous lithium ion secondary battery having the same |
| JP2009123687A (en) * | 2007-10-26 | 2009-06-04 | Nitto Denko Corp | Separator for battery, and nonaqueous lithium-ion secondary battery |
| CN102422466A (en) * | 2009-05-11 | 2012-04-18 | 奈克松有限公司 | Binder for lithium ion rechargeable battery cells |
| JP2012527069A (en) * | 2009-05-11 | 2012-11-01 | ネグゼオン・リミテッド | Lithium ion rechargeable battery cell |
| CN102668171A (en) * | 2009-11-19 | 2012-09-12 | 吉列公司 | Alkaline battery separators with ion-trapping molecules |
| WO2012011555A1 (en) * | 2010-07-23 | 2012-01-26 | 日本ゼオン株式会社 | Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery |
| JPWO2012011555A1 (en) * | 2010-07-23 | 2013-09-09 | 日本ゼオン株式会社 | Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery |
| CN103119755A (en) * | 2010-07-23 | 2013-05-22 | 日本瑞翁株式会社 | Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery |
| CN103119755B (en) * | 2010-07-23 | 2015-07-15 | 日本瑞翁株式会社 | Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery |
| JP2012089411A (en) * | 2010-10-21 | 2012-05-10 | Nippon Zeon Co Ltd | Cathode composition for lithium-ion secondary battery, cathode for lithium-ion secondary battery, and lithium-ion secondary battery |
| US9172076B2 (en) | 2011-01-11 | 2015-10-27 | Etv Energy Ltd. | Membranes suitable for use as separators and electrochemical cells including such separators |
| WO2012095805A1 (en) * | 2011-01-11 | 2012-07-19 | Etv Energy Ltd. | Membranes suitable for use as separators and electrochemical cells including such separators |
| US20130149588A1 (en) * | 2011-12-07 | 2013-06-13 | Arnd Garsuch | Electrochemical cells comprising chelate ligands |
| JP2015524601A (en) * | 2013-01-28 | 2015-08-24 | エルジー・ケム・リミテッド | Lithium secondary battery |
| US9882239B2 (en) | 2013-01-28 | 2018-01-30 | Lg Chem, Ltd. | Composition for gel polymer electrolyte and lithium secondary battery including the same |
| US10297860B2 (en) | 2013-01-28 | 2019-05-21 | Lg Chem, Ltd. | Lithium secondary battery |
| JP2015002167A (en) * | 2013-06-14 | 2015-01-05 | 上海緑孚新能源科技有限公司Ｇｒｅｅｎｆｕｌ Ｎｅｗ Ｅｎｅｒｇｙ Ｃｏ．，Ｌｔｄ． | Secondary battery |
| CN105474339A (en) * | 2013-08-22 | 2016-04-06 | 康宁股份有限公司 | Separator based on fibrous ceramic material for ultracapacitors, EDLC, hybrid capacitor, fuel cell and battery |
| CN110050365A (en) * | 2016-12-13 | 2019-07-23 | 汉高股份有限及两合公司 | Improved secondary lithium battery and lithium electrode for capacitors composition |
| JP2020513678A (en) * | 2016-12-13 | 2020-05-14 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Improved lithium ion secondary battery and lithium capacitor electrode composition |
| CN110050365B (en) * | 2016-12-13 | 2023-04-28 | 汉高股份有限及两合公司 | Improved secondary lithium ion battery and lithium capacitor electrode compositions |
| US11791468B2 (en) * | 2016-12-13 | 2023-10-17 | Henkel Ag & Co. Kgaa | Secondary Li ion battery and Li capacitor electrode compositions |
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