CN104934646A - Method for improving security of ternary-material polymer lithium ion battery - Google Patents

Method for improving security of ternary-material polymer lithium ion battery Download PDF

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Publication number
CN104934646A
CN104934646A CN201410107991.3A CN201410107991A CN104934646A CN 104934646 A CN104934646 A CN 104934646A CN 201410107991 A CN201410107991 A CN 201410107991A CN 104934646 A CN104934646 A CN 104934646A
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ion battery
ternary
positive electrode
material polymer
baso
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CN201410107991.3A
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汪超
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Shenzhen OptimumNano Energy Co Ltd
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Shenzhen OptimumNano Energy Co Ltd
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    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention discloses a method for improving the security of a ternary-material polymer lithium ion battery, and the method comprises the following five steps: an appropriate amount of lithium iron phosphate is doped into a ternary positive electrode material, on the basis of an electrolyte system in the prior art, GBL1.4-butyrolactone, FEC fluorinated propylene carbonate, and EFE fluoroether additive in a certain proportion are added; a negative electrode ending blank copper foil is emptily coiled for three circles; a diaphragm is coated with AL2O3 nano-ceramic; the positive electrode is doped with BaSO; and the like. Compared with the prior art, by use of the method of optimizing of the molecular structure of the positive electrode, expanding of the electrolyte temperature range, improvement of the structure of the negative ending blank copper, coating of the diaphragm with the AL2O3 nano-ceramic and doping of the positive electrode with BaSO and the like, thermodynamic and dynamical stability and high-temperature performance and puncturing, extrusion and falling safety standards can be integrally improved, and healthy development of the ternary-material polymer lithium ion battery in electric vehicles and other fields can be ensured.

Description

A kind of method improving the fail safe of ternary material polymer Li-ion battery
[technical field]
The present invention relates to field of lithium ion battery, particularly relate to a kind of method improving the fail safe of ternary material polymer Li-ion battery.
[background technology]
In automobile power cell field, most widely used positive electrode mainly contains ternary (nickel manganese cobalt acid lithium), LiFePO4, LiMn2O4.The high gram volume performance that ternary material has LiMn2O4 incomparable and long circulating performance, and the incomparable cryogenic property of LiFePO4 and high rate performance.But its fail safe fundamentally constrains the application on automobile power cell field.
The basic reason of ternary material poor stability is:
1: the caloric value of ternary wants high more than LiFePO4.The deoxidation temperature of ternary material is 200 DEG C, and exothermic energy is more than 800J/g, and the deoxidation temperature of LiFePO4 is 270 DEG C, and exothermic energy is only 124J/g, and more than 400 DEG C are just decomposed on a large scale;
2: ternary material is very active, has very strong oxidizability, meeting and the electrolyte solvent generation redox reaction with reproducibility.Positive pole is more active, and oxidizability is stronger, then reaction Shaoxing opera is strong, more easily causes security incident.The oxidizability of LiFePO4 is faint, seldom can cause security incident;
3: ternary material is the same with cobalt acid lithium, when being full of electricity (cut-off upper voltage limit 4.2V), the lithium Li+ in positive electrode still also has residue.If now charging voltage continues to raise, remaining lithium Li+ so in nickel-cobalt lithium manganate cathode material will continue deintercalation, trip is to negative pole, and the position that now can hold lithium Li+ in negative material has been filled, and lithium Li+ can only separate out on its surface in a metallic form and form lithium metal.Because lithium metal is very easy to be agglomerated into branch shape Li dendrite at surface deposition, thus pierce through barrier film, cause both positive and negative polarity direct short-circuit; On the other hand, lithium metal is very active, understands directly and electrolyte exothermic heat of reaction; Meanwhile, the fusing of lithium metal is quite low, even if surface metal Li dendrite does not pierce through barrier film, as long as temperature is slightly high, the battery such as caused owing to discharging heats up, and lithium metal will melt, thus by both positive and negative polarity short circuit, causes security incident.And lithium ion batteries for automobiles group needs a large amount of single battery core PACK assemblings, therefore battery pack volume is large, and its thermal diffusivity becomes poorer than single battery core, fail safe significantly declines especially, when ternary lithium ion battery is after maximization, along with the rising of temperature, have the danger of Fire Overheat or blast.In a word, ternary material is when charging voltage is too high, such as when baffle lost efficacy, there is great potential safety hazard, and the capacity of power lithium-ion battery is high, the destructiveness caused will be very large.
In sum, because the cylindrical lithium ion battery of just very ternary (nickel manganese cobalt acid lithium) material is often while meeting cycle life, high temperature performance, security performance is as not up to standard in punctured, extruding, fall etc., real effective breakthrough and progress cannot be obtained always, become its basic factor for energy source of car power of restriction.In view of this, be necessary in fact to provide a kind of method improving the fail safe of ternary material polymer Li-ion battery to overcome above-mentioned defect.
[summary of the invention]
The object of this invention is to provide a kind of method improving the fail safe of ternary material polymer Li-ion battery, it effectively improves the high temperature safety of ternary battery.
To achieve these goals, the present invention adopts following technical scheme: a kind of method improving the fail safe of ternary material polymer Li-ion battery, and it comprises five steps, and appropriate LiFePO4 mixes in tertiary cathode material by the first step; Second step is at existing electrolyte system, i.e. EC, EMC, DEC, PC, LiPF 6the basis of lithium salts adds a certain proportion of GBL1.4-butyrolactone, FEC fluoropropylene carbonate, EFE fluoro-ether additive; The 3rd step blank Copper Foil blank coil three that finished up by negative pole encloses; 4th step is by AL 2o 3nano ceramics coating barrier film; 5th step is at doping in positive electrode BaSO.
Improving as a kind of one improving the method for ternary material polymer Li-ion battery fail safe of the present invention, the gram volume of described LiFePO4 powder is necessary>=130mAh/g, compacted density>=2.2g/cm 3, LiFePO4 powder and triad fraction are 1: 9 ~ 2: 8, BaSO 4the ratio of powder is 1 ~ 5% of dry powder total amount.
Improve as a kind of one improving the method for ternary material polymer Li-ion battery fail safe of the present invention, described AL 2o 3the coat of nano ceramics coating barrier film is 4 ~ 8um.
LiFePO 4 material has orderly rhombic system olivine structural, in the olivine crystal structure of LiFePO 4 material uniqueness, lithium ion has two-dimentional mobility, energy free deintercalation during discharge and recharge, in addition, strong P-O covalent bond forms the three-dimensional stereochemistry key of delocalization, LiFePO 4 material is made to have very strong thermodynamics and kinetics stability, especially not easily releasing oxygen, LiFePO 4 material battery still can reach good stability under high temperature more than 400 DEG C, can not because overcharging, temperature is too high, short circuit, clash into and produce blast or burning, ensure that the high security of battery inherence.
A certain proportion of GBL, FEC, EFE fluoro-ether additive is added in existing electrolyte system, because GBL1.4 mono-butyrolactone lower limit fusing point is only-45 DEG C, upper limit fusing point, up to 204 DEG C, had both widened the temperature range of electrolyte, strengthened again electrolyte stability at high temperature; And FEC fluoropropylene carbonate mixes in electrolyte, can make to form densification, homogeneous SEI at negative electrode surface during battery initial charge, inhibit the decomposition-reduction of electrolyte simultaneously, hinder the side reactions such as the decomposition-reduction that electrolyte at high temperature occurs; Meanwhile, after adding EFE fluoro-ether additive, electrolyte flash-point can rise along with added ratio, improves the security performance under electrolyte high temperature.
The frame mode that the blank Copper Foil blank coil three that finished up by negative pole encloses can ensure battery core by external force extruding and puncture and short circuit time, empty around Copper Foil define closed-loop path big current can be made to be shunted, reduce caloric value, also no longer there is side reaction (positive electrode decomposition, electrolyte decomposition) thereupon, so can ensure that short circuit can not cause security implication.
AL 2the advantage of the more naked barrier film of O3 nano ceramics coating barrier film: 1: the closed pore temperature maintaining naked barrier film is constant, improves fusing-off temperature; 2: the acupuncture intensity improving barrier film; 3: easily growing Li dendrite near negative pole side, thus piercing through barrier film.And the ceramic layer of membrane surface contributes to the acupuncture intensity of barrier film, stop Li dendrite to the destruction of polyalkene diaphragm.
BaSO 4good insulating material, when having huge current flow when battery short circuit by anode electrode, BaSO 4the conduction of lithium ion between active material particle can be hindered, thus reduce the discharging current of battery, therefore play safeguard protection effect.
The invention has the beneficial effects as follows: the molecular structure optimizing positive pole by adding LiFePO 4 material, makes battery have very strong thermodynamics and kinetics stability; Add a certain proportion of GBL, FEC, EFE fluoro-ether additive in the electrolytic solution, not only widen the temperature range of electrolyte, strengthen electrolyte stability at high temperature, inhibit the decomposition-reduction of electrolyte simultaneously, hinder the side reactions such as the decomposition-reduction that electrolyte at high temperature occurs; To finish up the structure of blank copper by improving negative pole, ensure that battery core is can not cause security implication by external force extruding and puncture during short circuit; Barrier film applies AL 2o3 nano ceramics, improves barrier film fusing-off temperature and ceramic acupuncture intensity; The method of doping in positive electrode BaSO, prevents battery lithium ion conduction between active material particle when short circuit.The safety standard promote the high-temperature behavior of battery and puncture on the whole by series of steps, extruding, fall, ensure that the benign development of ternary material polymer Li-ion battery in fields such as electric automobiles.
[embodiment]
Below in conjunction with case study on implementation, the invention will be further described:
A kind of method improving the fail safe of ternary material polymer Li-ion battery of the present invention, it comprises five steps, and appropriate LiFePO4 mixes in tertiary cathode material by the first step; Second step is at existing electrolyte system, i.e. EC, EMC, DEC, PC, LiPF 6the basis of lithium salts adds a certain proportion of GBL1.4-butyrolactone, FEC fluoropropylene carbonate, EFE fluoro-ether additive; The 3rd step blank Copper Foil blank coil three that finished up by negative pole encloses; 4th step is by AL 2o 3nano ceramics coating barrier film; 5th step is at doping in positive electrode BaSO.
In first step, the gram volume of described LiFePO4 powder is necessary>=130mAh/g, compacted density>=2.2g/cm 3, LiFePO4 powder and triad fraction are 1: 9 ~ 2: 8, BaSO 4the ratio of powder is 1 ~ 5% of dry powder total amount, in the 4th step, and described AL 2o 3the coat of nano ceramics coating barrier film is 4 ~ 8um.
LiFePO 4 material has orderly rhombic system olivine structural, in the olivine crystal structure of LiFePO 4 material uniqueness, lithium ion has two-dimentional mobility, energy free deintercalation during discharge and recharge, in addition, strong P-O covalent bond forms the three-dimensional stereochemistry key of delocalization, LiFePO 4 material is made to have very strong thermodynamics and kinetics stability, especially not easily releasing oxygen, LiFePO 4 material battery still can reach good stability under high temperature more than 400 DEG C, can not because overcharging, temperature is too high, short circuit, clash into and produce blast or burning, ensure that the high security of battery inherence.
A certain proportion of GBL, FEC, EFE fluoro-ether additive is added in existing electrolyte system, because GBL1.4-butyrolactone lower limit fusing point is only-45 DEG C, upper limit fusing point, up to 204 DEG C, had both widened the temperature range of electrolyte, strengthened again electrolyte stability at high temperature; And FEC fluoropropylene carbonate mixes in electrolyte, can make to form densification, homogeneous SEI at negative electrode surface during battery initial charge, inhibit the decomposition-reduction of electrolyte simultaneously, hinder the side reactions such as the decomposition-reduction that electrolyte at high temperature occurs; Meanwhile, after adding EFE fluoro-ether additive, electrolyte flash-point can rise along with added ratio, improves the security performance under electrolyte high temperature.
The frame mode that the blank Copper Foil blank coil three that finished up by negative pole encloses can ensure battery core by external force extruding and puncture and short circuit time, empty around Copper Foil define closed-loop path big current can be made to be shunted, reduce caloric value, also no longer there is side reaction (positive electrode decomposition, electrolyte decomposition) thereupon, so can ensure that short circuit can not cause security implication.
AL 2the advantage of the more naked barrier film of O3 nano ceramics coating barrier film: 1: the closed pore temperature maintaining naked barrier film is constant, improves fusing-off temperature; 2: the acupuncture intensity improving barrier film; 3: easily growing Li dendrite near negative pole side, thus piercing through barrier film.And the ceramic layer of membrane surface contributes to the acupuncture intensity of barrier film, stop Li dendrite to the destruction of polyalkene diaphragm.
BaSO 4good insulating material, when having huge current flow when battery short circuit by anode electrode, BaSO 4the conduction of lithium ion between active material particle can be hindered, thus reduce the discharging current of battery, therefore play safeguard protection effect.
A kind of method improving the fail safe of ternary material polymer Li-ion battery of the present invention, be not restricted to described in specification and execution mode, therefore additional advantage and amendment can easily be realized for the personnel of familiar field, therefore when not deviating from the spirit and scope of the universal that claim and equivalency range limit, the present invention is not limited to specific details and representational equipment.

Claims (3)

1. improve a method for ternary material polymer Li-ion battery fail safe, it is special is, the method comprises five steps, and appropriate LiFePO4 mixes in tertiary cathode material by the first step; Second step is at existing electrolyte system, i.e. EC, EMC, DEC, PC, LiPF 6the basis of lithium salts adds a certain proportion of GBL1.4-butyrolactone, FEC fluoropropylene carbonate, EFE fluoro-ether additive; The 3rd step blank Copper Foil blank coil three that finished up by negative pole encloses; 4th step is by AL 2o 3nano ceramics coating barrier film; 5th step is at doping in positive electrode BaSO.
2. a kind of method improving the fail safe of ternary material polymer Li-ion battery according to claim 1, is characterized in that, the gram volume of described LiFePO4 powder is necessary>=and 130mAh/g, compacted density>=2.2g/cm 3, LiFePO4 powder and triad fraction are 1: 9 ~ 2: 8, BaSO 4the ratio of powder is 1 ~ 5% of dry powder total amount.
3. a kind of method improving the fail safe of ternary material polymer Li-ion battery according to claim 1, is characterized in that, described AL 2o 3the coat of nano ceramics coating barrier film is 4 ~ 8um.
CN201410107991.3A 2014-03-21 2014-03-21 Method for improving security of ternary-material polymer lithium ion battery Pending CN104934646A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105489843A (en) * 2015-12-29 2016-04-13 湖北宇电能源科技股份有限公司 Manufacturing method for safe lithium ion power battery positive plate
CN105529500A (en) * 2015-12-29 2016-04-27 湖北宇电能源科技股份有限公司 Manufacturing method for safe lithium ion power battery
CN107579209A (en) * 2017-07-22 2018-01-12 深圳卓朗新能源科技有限公司 A kind of high security ter-polymers lithium ion battery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1251215A (en) * 1997-02-28 2000-04-19 旭化成工业株式会社 Nonaqueous secondary battery and method for mfg. same
JP2004296360A (en) * 2003-03-28 2004-10-21 Sakai Chem Ind Co Ltd Nickel hydroxide particle for alkaline secondary battery cathode active substance and its manufacturing method
CN102005596A (en) * 2009-08-27 2011-04-06 Sb锂摩托有限公司 Rechargeable secondary battery having improved safety against puncture and collapse
CN102306730A (en) * 2011-08-08 2012-01-04 能一郎科技股份有限公司 Method for improving safety of high-capacity lithium ion power battery
CN102306833A (en) * 2011-08-17 2012-01-04 深圳新宙邦科技股份有限公司 Flame retardant type non-aqueous electrolyte solution and battery thereof
CN103035866A (en) * 2013-01-09 2013-04-10 厦门大学 Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1251215A (en) * 1997-02-28 2000-04-19 旭化成工业株式会社 Nonaqueous secondary battery and method for mfg. same
JP2004296360A (en) * 2003-03-28 2004-10-21 Sakai Chem Ind Co Ltd Nickel hydroxide particle for alkaline secondary battery cathode active substance and its manufacturing method
CN102005596A (en) * 2009-08-27 2011-04-06 Sb锂摩托有限公司 Rechargeable secondary battery having improved safety against puncture and collapse
CN102306730A (en) * 2011-08-08 2012-01-04 能一郎科技股份有限公司 Method for improving safety of high-capacity lithium ion power battery
CN102306833A (en) * 2011-08-17 2012-01-04 深圳新宙邦科技股份有限公司 Flame retardant type non-aqueous electrolyte solution and battery thereof
CN103035866A (en) * 2013-01-09 2013-04-10 厦门大学 Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105489843A (en) * 2015-12-29 2016-04-13 湖北宇电能源科技股份有限公司 Manufacturing method for safe lithium ion power battery positive plate
CN105529500A (en) * 2015-12-29 2016-04-27 湖北宇电能源科技股份有限公司 Manufacturing method for safe lithium ion power battery
CN107579209A (en) * 2017-07-22 2018-01-12 深圳卓朗新能源科技有限公司 A kind of high security ter-polymers lithium ion battery

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