CN103972503A - Cathode material for lithium ion battery - Google Patents
Cathode material for lithium ion battery Download PDFInfo
- Publication number
- CN103972503A CN103972503A CN201410134599.8A CN201410134599A CN103972503A CN 103972503 A CN103972503 A CN 103972503A CN 201410134599 A CN201410134599 A CN 201410134599A CN 103972503 A CN103972503 A CN 103972503A
- Authority
- CN
- China
- Prior art keywords
- lithium
- battery
- ion batteries
- anode material
- additive
- 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.)
- Granted
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000010406 cathode material Substances 0.000 title abstract 4
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000011149 active material Substances 0.000 claims abstract description 5
- 239000010405 anode material Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract description 3
- 230000003111 delayed effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
Abstract
The invention discloses a cathode material for a lithium ion battery. The cathode material for the lithium ion battery comprises an active material and an additive, wherein the additive adopts LiXMYMn1-YO2, x is larger than or equal to 0.85 and smaller than or equal to 1.1, and y is larger than or equal to 0.7 and smaller than or equal to 0.9. According to the cathode material prepared by adding the additive, a cathode potential can be stabilized under the over-discharge condition, so that the cathode potential rises slowly, short circuit caused by the fact that the cathode potential quickly rises to a copper evolution potential is avoided, and the over-discharge phenomenon is prevented or delayed.
Description
Technical field:
The present invention relates to lithium ion battery material technical field, be specifically related to a kind of anode material for lithium-ion batteries.
Background technology:
Compared with other storage batterys, the advantage of lithium ion battery is that energy density is high, open circuit voltage is high, specific capacity is large, self-discharge rate is low, the life-span is long, there is no memory effect, the application of lithium ion battery is from space technology at present, aviation, the military fields such as guided missile expand to industrial sphere of life, be widely used in mobile phone, notebook computer, the miniaturized electronicss such as digital camera, particularly lithium battery is widely used gradually as electrokinetic cell in recent years, be applied in energy storage, in the fields such as electric motor car.The cycle life of electrokinetic cell to lithium battery, energy density, discharge capabilities etc. propose higher requirement.
In order to improve the fail safe of lithium ion battery, prevent battery under incorrect service condition or over-discharge situation that other reasons causes, except additional protection circuit, also wish that battery itself has certain protective capacities.
Summary of the invention:
In order to make up prior art problem, the object of this invention is to provide a kind of anode material for lithium-ion batteries, make lithium ion battery under over-discharge situation, have better performance, improve the fail safe of lithium ion battery.
Technical scheme of the present invention is as follows:
Anode material for lithium-ion batteries, is characterized in that: described anode material for lithium-ion batteries comprises active material and additive; Described additive is Li
xm
ymn
1-Yo
2; Wherein 0.85≤x≤1.1,0.7≤y≤0.9.
Described anode material for lithium-ion batteries, is characterized in that: the M in described additive is at least one in Fe, Zn.
Described anode material for lithium-ion batteries, is characterized in that: described additive is Li
0.85fe
0.7mn
0.3o
2, Li
1.1fe
0.9mn
0.1o
2, Li
0.85zn
0.7mn
0.3o
2, Li
1.1zn
0.9mn
0.1o
2in one or more.
Described anode material for lithium-ion batteries, is characterized in that, taking the percentage composition of anode material for lithium-ion batteries as benchmark, described additive level is no more than 20wt%.
Described anode material for lithium-ion batteries, is characterized in that, taking the percentage composition of anode material for lithium-ion batteries as benchmark, described additive level is 7～10wt%.
Described anode material for lithium-ion batteries, is characterized in that, described additive is solid particle, and particle diameter is 0.5～9um.
Described anode material for lithium-ion batteries, is characterized in that, described active material is LiFePO4.
Advantage of the present invention is:
The present invention is by increasing the positive electrode that makes of additive, can stable negative electrode potential under over-discharge situation, and make negative potential increase very slow, be unlikely to be raised to fast and analyse copper current potential and cause short circuit, play the effect that prevents or delay overdischarge.
Embodiment:
In order to make technical problem solved by the invention, technical scheme, beneficial effect is clearer, and below in conjunction with embodiment and embodiment, the present invention is described in further detail.
The present invention provides a kind of lithium ion cell positive simultaneously, is coated in positive electrode collector on after being mixed with slurry by anode material for lithium-ion batteries provided by the present invention together with conductive agent, binding agent and solvent, and drying, calendering prepare.In the time preparing anode sizing agent by anode material for lithium-ion batteries provided by the present invention, conductive agent used, binding agent and solvent etc. can be various material known in those skilled in the art, ratio the present invention of anodal activity, conductive agent, binding agent and solvent is also not particularly limited, can adjust flexibly material concentration according to the viscosity of the slurry coating of the composition of battery electrode positive electrode, binding agent and positive electrode to be prepared and the requirement of operability, mode is conventionally known to one of skill in the art.
Embodiment 1
1) anodal preparation:
By 70g iron phosphate serving as positive active material, 20g additive Li
0.85fe
0.7mn
0.3o
2, 3g polyfluortetraethylene of binding element, 4g conductive agent SP, 0.5g dispersant PVP, 102g solvent sulfolane mix and blend, is coated on and on aluminium foil, dries roll-in and cut and make positive plate.
2) preparation of negative pole
By 40g native graphite, 1g polyfluortetraethylene of binding element, 100g deionized water mix and blend, is coated on and on Copper Foil, dries roll-in and cut and make negative plate.
3) preparation of battery
By just above-mentioned, negative pole is wound into the pole piece of a lithium ion battery in polypropylene screen, add electrolyte respectively, injects battery aluminum shell, and sealing changes into and makes lithium ion battery.
Embodiment 2
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, that different is the Li that the additive in positive electrode is 14g
1.1fe
0.9mn
0.1o
2, the LiFePO4 that positive electrode active materials is 76g.
Embodiment 3
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, that different is the Li that the additive in positive electrode is 20g
0.85zn
0.7mn
0.3o
2, the LiFePO4 that positive electrode active materials is 70g.
Embodiment 4
Adopt the method identical with embodiment 1 and step preparation positive pole, negative pole and battery, that different is the Li that the additive in positive electrode is 14g
1.1zn
0.9mn
0.1o
2, the LiFePO4 that positive electrode active materials is 76g.
Comparative example 1
4) anodal preparation:
By 90g iron phosphate serving as positive active material, 3g polyfluortetraethylene of binding element, 4g conductive agent SP, 0.5g dispersant PVP, 102g solvent sulfolane mix and blend, is coated on and on aluminium foil, dries roll-in and cut and make positive plate.
5) preparation of negative pole
By 40g native graphite, 1g polyfluortetraethylene of binding element, 100g deionized water mix and blend, is coated on and on Copper Foil, dries roll-in and cut and make negative plate.
6) preparation of battery
The pole piece that respectively above-mentioned positive and negative electrode is wound into a lithium ion battery in polypropylene screen, adds electrolyte, injects battery aluminum shell, and sealing changes into and makes lithium ion battery.
Electrochemical property test:
Battery prepared by embodiment 1～4 and comparative example 1 charges to 4V with 0.1C, shelves 10 minutes, is then discharged to 2.0V with 0.1C; Then this battery is charged to 3.4V with 1C, shelve 10 minutes, then discharge into 0V with 1C.Record discharge capacity and the battery discharge capacity when 2.0V above of battery under 2.0-1.0V, the ratio value of the discharge capacity by battery in the time that the shared 2.0V of the discharge capacity under 2.0-1.0V is above is recorded in table 1.Meanwhile, when battery discharge is arrived to 1.0V, the potential value of battery cathode is recorded in table 1.
Table 1
Can be found out by data in table 1, with respect to battery, the discharge capacity proportion under the above condition of 2.0V is higher to the discharge capacity of the battery of embodiment 1～4 under 2.0-1.0V condition, and the capacity that comparative example 1 can be emitted under 2.0～1.0V condition is low-down, put under condition can stable negative electrode potential crossing for the battery that embodiment 1～4 is described, make negative pole current potential be unlikely to be raised to fast and analyse copper current potential, cause short circuit, thereby play the effect that prevents or delay overdischarge; Simultaneously, in the time that battery discharge arrives 1.0V, in comparative example, negative pole current potential is higher than 0.6V, at negative pole current potential, during higher than 0.6V, negative pole forms solid electrolyte interface film, thereby battery performance is obviously worsened, and easily cause safety problem, and negative pole current potential, all lower than 0.6V, can't exist this problem in embodiment 1～4, battery is significantly improved in the security performance under condition to one's heart's content.Be to be understood that, above-mentioned embodiment and embodiment only, for explaining the present invention, are not limited to the present invention.
Claims (7)
1. an anode material for lithium-ion batteries, is characterized in that: described anode material for lithium-ion batteries comprises active material and additive; Described additive is Li
xm
ymn
1-Yo
2; Wherein 0.85≤x≤1.1,0.7≤y≤0.9.
2. anode material for lithium-ion batteries according to claim 1, is characterized in that: the M in described additive is at least one in Fe, Zn.
3. anode material for lithium-ion batteries according to claim 2, is characterized in that: described additive is Li
0.85fe
0.7mn
0.3o
2, Li
1.1fe
0.9mn
0.1o
2, Li
0.85zn
0.7mn
0.3o
2, Li
1.1zn
0.9mn
0.1o
2in one or more.
4. according to the anode material for lithium-ion batteries described in claim 1 ~ 3 any one, it is characterized in that, taking the percentage composition of anode material for lithium-ion batteries as benchmark, described additive level is no more than 20wt%.
5. according to the anode material for lithium-ion batteries described in claim 1 ~ 3 any one, it is characterized in that, taking the percentage composition of anode material for lithium-ion batteries as benchmark, described additive level is 7 ~ 10wt%.
6. according to the anode material for lithium-ion batteries described in claim 1 ~ 3 any one, it is characterized in that, described additive is solid particle, and particle diameter is 0.5 ~ 9um.
7. anode material for lithium-ion batteries according to claim 1, is characterized in that, described active material is LiFePO4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410134599.8A CN103972503B (en) | 2014-04-02 | 2014-04-02 | A kind of anode material for lithium-ion batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410134599.8A CN103972503B (en) | 2014-04-02 | 2014-04-02 | A kind of anode material for lithium-ion batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103972503A true CN103972503A (en) | 2014-08-06 |
| CN103972503B CN103972503B (en) | 2016-04-13 |
Family
ID=51241758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410134599.8A Active CN103972503B (en) | 2014-04-02 | 2014-04-02 | A kind of anode material for lithium-ion batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103972503B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410189A (en) * | 2016-12-19 | 2017-02-15 | 苏州格瑞动力电源科技有限公司 | Lithium ion battery positive pole material |
| CN106935413A (en) * | 2017-03-24 | 2017-07-07 | 合肥羿振电力设备有限公司 | A kind of capacitor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030003369A1 (en) * | 2000-04-26 | 2003-01-02 | Hongli Dai | High performance lithium or lithium ion cell |
| CN101728512A (en) * | 2009-11-16 | 2010-06-09 | 苏州星恒电源有限公司 | Lithium battery anode material and preparation method thereof |
| CN101944599A (en) * | 2010-09-15 | 2011-01-12 | 宁波科博特钴镍有限公司 | Preparation method of cobalt-based material |
| CN102386409A (en) * | 2011-11-03 | 2012-03-21 | 湖南丰源业翔晶科新能源股份有限公司 | Paste for cathode of lithium iron phosphate lithium ion battery |
| CN102779998A (en) * | 2012-07-19 | 2012-11-14 | 东莞新能源科技有限公司 | Lithium ion monomer battery capable of preventing overdischarge |
-
2014
- 2014-04-02 CN CN201410134599.8A patent/CN103972503B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030003369A1 (en) * | 2000-04-26 | 2003-01-02 | Hongli Dai | High performance lithium or lithium ion cell |
| CN101728512A (en) * | 2009-11-16 | 2010-06-09 | 苏州星恒电源有限公司 | Lithium battery anode material and preparation method thereof |
| CN101944599A (en) * | 2010-09-15 | 2011-01-12 | 宁波科博特钴镍有限公司 | Preparation method of cobalt-based material |
| CN102386409A (en) * | 2011-11-03 | 2012-03-21 | 湖南丰源业翔晶科新能源股份有限公司 | Paste for cathode of lithium iron phosphate lithium ion battery |
| CN102779998A (en) * | 2012-07-19 | 2012-11-14 | 东莞新能源科技有限公司 | Lithium ion monomer battery capable of preventing overdischarge |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410189A (en) * | 2016-12-19 | 2017-02-15 | 苏州格瑞动力电源科技有限公司 | Lithium ion battery positive pole material |
| WO2018113439A1 (en) * | 2016-12-19 | 2018-06-28 | 苏州格瑞动力电源科技有限公司 | Positive electrode material for lithium ion battery |
| CN106935413A (en) * | 2017-03-24 | 2017-07-07 | 合肥羿振电力设备有限公司 | A kind of capacitor |
| CN106935413B (en) * | 2017-03-24 | 2018-09-11 | 合肥羿振电力设备有限公司 | A kind of capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103972503B (en) | 2016-04-13 |
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Effective date of registration: 20230613 Address after: 238300 hi tech new material industrial park, Shijian Town, Wuwei County, Wuhu City, Anhui Province Patentee after: Anhui Qixin New Material Technology Co.,Ltd. Address before: 241000 floor 3, building 4, phase II, Service Outsourcing Industrial Park, Wuhu high tech Industrial Development Zone, Anhui Province (No. 717, south Zhongshan Road) Patentee before: ANHUI AND NEW ENERGY MATERIALS CO.,LTD. |
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