CN102903958A - Method for improving cycle performance and rate capability of lithium titanate battery - Google Patents
Method for improving cycle performance and rate capability of lithium titanate battery Download PDFInfo
- Publication number
- CN102903958A CN102903958A CN2012103957862A CN201210395786A CN102903958A CN 102903958 A CN102903958 A CN 102903958A CN 2012103957862 A CN2012103957862 A CN 2012103957862A CN 201210395786 A CN201210395786 A CN 201210395786A CN 102903958 A CN102903958 A CN 102903958A
- Authority
- CN
- China
- Prior art keywords
- lithium titanate
- battery
- titanate battery
- cycle performance
- high rate
- 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.)
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims description 6
- 150000003457 sulfones Chemical class 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- -1 benzene sulfone Chemical class 0.000 claims 1
- 239000002000 Electrolyte additive Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 230000008961 swelling Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 206010016766 flatulence Diseases 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for improving the cycle performance and the rate capability of a lithium titanate battery. The main improvement is that additives including a stabilizer and a gas elimination agent are added into an electrolyte of the battery; the temperature is controlled to be 5 to 60 DEG C in a formation process of the battery; 3-6 sections of ladder currents from low to high are adopted for formation charge; the current interval is 0.02 to 1C; the charging time of each stage is 1 to 4 hours; and the upper limit voltage is 1.9 to 3.2V. By the method, the problem of battery swelling is solved effectively by adopting a complete and reasonable formation process and by using the electrolyte additives; the corrosion of substrates of an anode and a cathode is restrained; and therefore, the cycle performance and the rate capability of the lithium titanate battery are improved, and the requirements of a power lithium battery are met.
Description
Technical field
The present invention relates to the lithium ion battery that negative pole is lithium titanate material, specifically relate to a kind of method that improves lithium titanate battery cycle performance and high rate performance.
Background technology
Saving petroleum resources, reduction of greenhouse gas discharge and air quality purification is the three challenges that world today's auto industry faces.Power battery technology always is the key of restriction Development of Electric Vehicles, and wherein the research of lithium-ions battery obtains more concerns and input.The application of lithium-ions battery on electric automobile just promoting it to the future development of safety, environmental protection, low cost and high-energy-density.Electric automobile requires that the lithium ion battery self-discharge rate is low, rapid charging performance good, overcharging resisting crosses that exoergic power is good, power density is high, have extended cycle life.
In recent years, up to 1.5 V, the lithium titanate of fail safe and cell excellent in cycle characteristics (Li4Ti5O12) had been subject to extensive concern to the lithium current potential.Li4Ti5O12 has " zero strain " characteristic that skeleton structure changes hardly in the charge and discharge process, embedding lithium current potential high (1.55 V vs. Li/Li+) and be difficult for causing that lithium metal is separated out, coulombic efficiency is high, lithium ion diffusion coefficient (10-8 cm2/s) is than the high order of magnitude of carbon negative pole.These good characteristics make it possessed power lithium-ion battery essential have extended cycle life, good rate capability, charging process faster, safer requirement.
In lithium titanate battery research, find that there is the flatulence problem in the battery take lithium titanate as negative material, so that the requirement of the cycle life of battery and high rate performance and dynamic lithium battery exists very large gap.
Want to bring into play the excellent properties of lithium titanate material, must solve battery flatulence and cause battery cycle life and the poor problem of high rate performance.
Summary of the invention
The objective of the invention is to overcome the at present weak point of the lithium battery take lithium titanate as negative material, a kind of method that improves lithium titanate battery cycle performance and high rate performance is provided, make lithium titanate battery can reach the requirement of dynamic lithium battery.
Technical scheme of the present invention is: add the additive that comprises stabilizer and gas remover in the electrolyte of lithium titanate battery, described stabilizer is one or more of fluorinated, nitrile and sulfone class organic compound; In the formation process of lithium titanate battery, the control temperature is-10～60 ℃, adopts 1～6 circulation, formation charging adopts 3～6 sections little rear large grading currents of elder generation, be 0.02C～1C between Current Zone, each charging interval in stage is 1～4 hour, and upper voltage limit is 1.9～3.2V.
Further scheme is: described fluorinated, nitrile and sulfone class organic compound for fluoridize cyclic carbonate, fluoridize linear carbonate, perfluorooctanoic acid, fourth dicyan, stupid sulfone; The addition of described additive is 0.5～2.0wt% of electrolyte; The described temperature that changes into is 5～60 ℃, and upper voltage limit is 2.0～2.8V.
Battery kept opened type, is subjected to a kind of state in pressure type, vacuum type, pregnant solution type, the barren liquor type when the present invention changed into.
Described method be applicable to positive electrode comprise in LiFePO4, LiMn2O4, ternary material and the LiMn2O4 doping ternary material one or more, the negative material lithium titanate is the surface lithium battery made of carbon coated or carbon coated material not.
Perfect, rational chemical synthesis technology that the present invention adopts, in the stage that changes into the moisture in the battery material is fully reacted, generate gas and discharge outside batteries, stop electrolyte at the last decomposition of positive pole by special electrolysis additive, can compoundly eliminate simultaneously the minimum gas that electrolyte decomposition produces, thoroughly solve battery flatulence problem.Because additive can neutralizing acid, can suppress the both positive and negative polarity matrix and be corroded.Thereby improve lithium titanate battery cycle life and high rate performance, so that the cycle life of battery is when bringing up to circulation 6000 times for 3000 times from less than, residual capacity still is more than 87%; 20C multiplying power discharging capacity and 1C discharge capacity ratio are also by bringing up to more than 78% below 65%.
Embodiment
Specify the present invention and battery testing result below by embodiment:
Do not relate in the lithium titanate battery manufacturing process part routinely technique carry out.
Claims (4)
1. method that improves lithium titanate battery cycle performance and high rate performance, it is characterized in that adding the additive that comprises stabilizer and gas remover in the electrolyte of lithium titanate battery, described stabilizer is one or more of fluorinated, nitrile and sulfone class organic compound; In the formation process of lithium titanate battery, the control temperature is-10～60 ℃, adopts 1～6 circulation, formation charging adopts 3～6 sections little rear large grading currents of elder generation, be 0.02C～1C between Current Zone, each charging interval in stage is 1～4 hour, and upper voltage limit is 1.9～3.2V.
2. a kind of method that improves lithium titanate battery cycle performance and high rate performance according to claim 1 is characterized in that: described fluorinated, nitrile and sulfone class organic compound for fluoridize cyclic carbonate, fluoridize linear carbonate, perfluorooctanoic acid, fourth dicyan, benzene sulfone.
3. a kind of method that improves lithium titanate battery cycle performance and high rate performance according to claim 1, it is characterized in that: the addition of described additive is 0.5～2.0wt% of electrolyte.
4. a kind of method that improves lithium titanate battery cycle performance and high rate performance according to claim 1, it is characterized in that: the described temperature that changes into is 5～60 ℃, and upper voltage limit is 2.0～2.8V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103957862A CN102903958A (en) | 2012-10-18 | 2012-10-18 | Method for improving cycle performance and rate capability of lithium titanate battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103957862A CN102903958A (en) | 2012-10-18 | 2012-10-18 | Method for improving cycle performance and rate capability of lithium titanate battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102903958A true CN102903958A (en) | 2013-01-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103957862A Pending CN102903958A (en) | 2012-10-18 | 2012-10-18 | Method for improving cycle performance and rate capability of lithium titanate battery |
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| CN (1) | CN102903958A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470572A (en) * | 2015-01-16 | 2016-04-06 | 万向A一二三系统有限公司 | Lithium titanate battery and formation method thereof |
| CN105470573A (en) * | 2015-01-16 | 2016-04-06 | 万向A一二三系统有限公司 | Lithium titanate battery with high safety performance |
| CN105470574A (en) * | 2015-01-16 | 2016-04-06 | 万向A一二三系统有限公司 | Lithium titanate battery with high cycle performance |
| CN106133986A (en) * | 2014-03-27 | 2016-11-16 | 大金工业株式会社 | Electrolyte and electrochemical device |
| CN108172919A (en) * | 2017-12-25 | 2018-06-15 | 北京国能电池科技有限公司 | Ternary lithium ion battery chemical synthesis technology and ternary lithium ion battery and preparation method thereof |
| CN109346772A (en) * | 2018-09-26 | 2019-02-15 | 东莞市杉杉电池材料有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
| CN109585923A (en) * | 2018-12-11 | 2019-04-05 | 广东永邦新能源股份有限公司 | A kind of lithium battery electrolytes and preparation method thereof |
| CN110518290A (en) * | 2019-09-24 | 2019-11-29 | 深圳睿蚁科技有限公司 | A method of improving lithium battery high rate performance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740816A (en) * | 2009-12-24 | 2010-06-16 | 苏州星恒电源有限公司 | Formation method of lithium ion secondary battery using lithium titanate as cathode |
| CN102280661A (en) * | 2011-06-27 | 2011-12-14 | 东莞新能源科技有限公司 | Lithium titanate battery and electrolyte thereof |
| CN102593513A (en) * | 2012-02-17 | 2012-07-18 | 深圳新宙邦科技股份有限公司 | Lithium ion secondary battery and electrolyte thereof |
-
2012
- 2012-10-18 CN CN2012103957862A patent/CN102903958A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740816A (en) * | 2009-12-24 | 2010-06-16 | 苏州星恒电源有限公司 | Formation method of lithium ion secondary battery using lithium titanate as cathode |
| CN102280661A (en) * | 2011-06-27 | 2011-12-14 | 东莞新能源科技有限公司 | Lithium titanate battery and electrolyte thereof |
| CN102593513A (en) * | 2012-02-17 | 2012-07-18 | 深圳新宙邦科技股份有限公司 | Lithium ion secondary battery and electrolyte thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106133986A (en) * | 2014-03-27 | 2016-11-16 | 大金工业株式会社 | Electrolyte and electrochemical device |
| US10355312B2 (en) | 2014-03-27 | 2019-07-16 | Daikin Industries, Ltd. | Electrolyte and electrochemical device |
| CN106133986B (en) * | 2014-03-27 | 2019-07-09 | 大金工业株式会社 | Electrolyte and electrochemical device |
| CN105470573B (en) * | 2015-01-16 | 2018-05-18 | 万向一二三股份公司 | A kind of lithium titanate battery of high safety performance |
| CN105470572B (en) * | 2015-01-16 | 2018-03-23 | 万向一二三股份公司 | A kind of lithium titanate battery and its chemical synthesizing method |
| CN105470574B (en) * | 2015-01-16 | 2018-05-18 | 万向一二三股份公司 | A kind of lithium titanate battery of high circulation performance |
| CN105470572A (en) * | 2015-01-16 | 2016-04-06 | 万向A一二三系统有限公司 | Lithium titanate battery and formation method thereof |
| CN105470574A (en) * | 2015-01-16 | 2016-04-06 | 万向A一二三系统有限公司 | Lithium titanate battery with high cycle performance |
| CN105470573A (en) * | 2015-01-16 | 2016-04-06 | 万向A一二三系统有限公司 | Lithium titanate battery with high safety performance |
| CN108172919A (en) * | 2017-12-25 | 2018-06-15 | 北京国能电池科技有限公司 | Ternary lithium ion battery chemical synthesis technology and ternary lithium ion battery and preparation method thereof |
| CN108172919B (en) * | 2017-12-25 | 2020-06-02 | 北京国能电池科技有限公司 | Ternary lithium ion battery formation process, ternary lithium ion battery and preparation method thereof |
| CN109346772A (en) * | 2018-09-26 | 2019-02-15 | 东莞市杉杉电池材料有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
| CN109585923A (en) * | 2018-12-11 | 2019-04-05 | 广东永邦新能源股份有限公司 | A kind of lithium battery electrolytes and preparation method thereof |
| CN110518290A (en) * | 2019-09-24 | 2019-11-29 | 深圳睿蚁科技有限公司 | A method of improving lithium battery high rate performance |
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Application publication date: 20130130 |