CN109638342A - A kind of lithium ion battery that high temperature performance can combine - Google Patents
A kind of lithium ion battery that high temperature performance can combine Download PDFInfo
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- CN109638342A CN109638342A CN201811553388.2A CN201811553388A CN109638342A CN 109638342 A CN109638342 A CN 109638342A CN 201811553388 A CN201811553388 A CN 201811553388A CN 109638342 A CN109638342 A CN 109638342A
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- Prior art keywords
- lithium ion
- ion battery
- high temperature
- combine
- lithium
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Classifications
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M4/58—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
-
- 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
In order to obtain under a kind of low temperature under high power performance and high temperature long circulating stability lithium ion battery, the invention discloses the lithium ion batteries that a kind of high temperature performance can combine, including anode, cathode, diaphragm and electrolyte, it is characterized by: the anode includes active material, binder and conductive agent, the active material accounts for the 95%~99.4% of positive gross mass, and the active material is LiFePO4, the LiFePO4The diameter of particle is less than 1 μm；The electrolyte includes organic solvent, lithium salts, anode additive and cathode additive agent.It the invention belongs to technical field of lithium ion, its advantage lies in being able to still have high power characteristic at -30 DEG C, and there is high cyclical stability at 55 DEG C.
Description
Technical field
The invention belongs to the lithium ions that technical field of lithium ion more particularly to a kind of high temperature performance can combine
Battery.
Background technique
As people are to the growing interest of environment and energy-saving and emission-reduction etc., lithium ion battery is due to high-energy-density, senior engineer
Make the advantages such as voltage, environmental-friendly, is used widely in life.Such as: mobile phone, digital camera, laptop, movement
Power supply, bluetooth headset.In addition, lithium ion battery obtains development and usage on unmanned plane and automobile, especially as automobile
The use of start and stop power supply.Oil consumption not only can be effectively reduced in utilization of the lithium ion battery on automobile, can also make automobilism
More rapidly, smooth.
However, application of the lithium ion battery on automobile must have under low temperature, long circulating is steady under high power performance and high temperature
It is qualitative.Currently, high temperature and cryogenic property are usually to be difficult to combine in existing lithium-ion battery system.Therefore, really
It is necessary to develop a kind of lithium ion battery that high temperature performance is excellent, lithium ion battery is promoted widely to apply on automobile.
Summary of the invention
The object of the present invention is to provide the lithium-ion electrics of long circulating stability under high power performance under a kind of low temperature and high temperature
Pond, the battery have high power characteristic at -30 DEG C, and have long circulating stability at 55 DEG C.
To achieve the goals above, the present invention adopts the following technical scheme that:
A kind of lithium ion battery that high temperature performance can combine, including anode, cathode, diaphragm and electrolyte, it is described
Anode includes active material, binder and conductive agent.
Further, the active material accounts for the 95%~99.4% of positive gross mass, and the active material is
LiFePO4, the LiFePO4The diameter of particle is less than 1 μm.
Further, the binder accounts for the 0.5%~3% of positive gross mass, the binder be Kynoar,
At least one of LA133 and polyacrylic acid.
Further, the conductive agent accounts for the 0.1%~2% of positive gross mass, and the conductive agent is carbon nanotube, graphite
At least one of alkene, acetylene black.
Further, the electrolyte includes organic solvent, lithium salts, anode additive and cathode additive agent.
Further, the organic solvent accounts for the 65%~87.8% of electrolyte gross mass, and it is total that the lithium salts accounts for electrolyte
The 12%~25% of quality, the anode additive account for the 0.1%~5% of electrolyte gross mass, and the cathode additive agent accounts for electricity
Solve the 0.1%~5% of liquid gross mass.
Further, the organic solvent includes cyclic solvent and linear solvents, the cyclic solvent and linear solvents
Mass ratio is 1~2:3.
Preferably, the cyclic solvent be ethylene carbonate, propene carbonate, fluorinated ethylene carbonate, gamma-butyrolacton and
One of gamma-valerolactone or multiple combinations；The linear solvents are dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, carbon
One of sour first propyl ester, ethyl propionate or multiple combinations.
Preferably, the lithium salts is lithium hexafluoro phosphate, double fluorine sulfimide lithiums, difluorine oxalic acid boracic acid lithium, bis- (trifluoromethyls
Sulphonyl) one of imine lithium and di-oxalate lithium borate or a variety of combinations.
Preferably, the anode additive is ethylene sulfite, in sulfuric acid vinyl ester, three (trimethyl silane) borates
One or more combinations, the cathode additive agent be 1,3- propene sultone, 1,3- propane sultone, ethylene carbonate
At least one in the double oxalic acid lithium phosphates of ethyl, sulfurous acid vinylethylene, difluorophosphate, difluoro, tetrafluoro oxalic acid lithium phosphate
Kind.
The present invention compared with the existing technology the utility model has the advantages that
The lithium ion battery that a kind of high temperature performance that the present invention records can combine, the LiFePO of small particle4Material
There is strong interaction with distinctive anode additive, formed fine and close and be conducive to the interfacial film that lithium ion passes through.Meanwhile it is logical
The introducing for crossing high conductivity conductive material reduces cell resistance, and the two combination can make battery have high power characteristic；
In addition, by the addition of cathode additive agent so that high temperature cyclic performance is obviously improved.
Specific embodiment
Below by exemplary embodiment, the present invention will be further elaborated；But the scope of the present invention should not limit to
In the range of embodiment, any variation or change without departing from present subject matter can be understood by the person skilled in the art,
All within protection scope of the present invention.
Specific embodiment 1:
A kind of lithium ion battery that high temperature performance can combine, including anode, cathode, diaphragm and electrolyte, it is described
Anode includes active material, binder and conductive agent.
Further, the active material accounts for the 95%~99.4% of positive gross mass, and the active material is
LiFePO4, the LiFePO4The diameter of particle is less than 1 μm.
Further, the binder accounts for the 0.5%~3% of positive gross mass, the binder be Kynoar,
At least one of LA133 and polyacrylic acid.
Further, the conductive agent accounts for the 0.1%~2% of positive gross mass, and the conductive agent is carbon nanotube, graphite
At least one of alkene, acetylene black.
Further, the electrolyte includes organic solvent, lithium salts, anode additive and cathode additive agent.
Further, the organic solvent accounts for the 65%~87.8% of electrolyte gross mass, and it is total that the lithium salts accounts for electrolyte
The 12%~25% of quality, the anode additive account for the 0.1%~5% of electrolyte gross mass, and the cathode additive agent accounts for electricity
Solve the 0.1%~5% of liquid gross mass.
Further, the organic solvent includes cyclic solvent and linear solvents, the cyclic solvent and linear solvents
Mass ratio is 1~2:3.
Preferably, the cyclic solvent be ethylene carbonate, propene carbonate, fluorinated ethylene carbonate, gamma-butyrolacton and
One of gamma-valerolactone or multiple combinations；The linear solvents are dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, carbon
One of sour first propyl ester, ethyl propionate or multiple combinations.
Preferably, the lithium salts is lithium hexafluoro phosphate, double fluorine sulfimide lithiums, difluorine oxalic acid boracic acid lithium, bis- (trifluoromethyls
Sulphonyl) one of imine lithium and di-oxalate lithium borate or a variety of combinations.
Preferably, the anode additive is ethylene sulfite, in sulfuric acid vinyl ester, three (trimethyl silane) borates
One or more combinations, the cathode additive agent be 1,3- propene sultone, 1,3- propane sultone, ethylene carbonate
At least one in the double oxalic acid lithium phosphates of ethyl, sulfurous acid vinylethylene, difluorophosphate, difluoro, tetrafluoro oxalic acid lithium phosphate
Kind.
Embodiment 1
A kind of lithium ion battery that high temperature performance can combine, including anode, cathode, diaphragm, electrolyte, it is described just
Pole includes active material, conductive agent and binder, and the active material is the LiFePO of 500nm partial size4, conductive agent is acetylene
Black, binder is Kynoar (PVDF), and the percentage that active material, conductive agent, binder account for positive gross mass is respectively
95%, 2%, 3%；The electrolyte includes organic solvent, lithium salts, anode additive, cathode additive agent, and the organic solvent is
Ethylene carbonate and ethyl propionate, the lithium salts are lithium hexafluoro phosphate, and the anode additive is ethylene sulfite, described negative
Pole additive is 1,3- propane sultone, and electrolyte composition ratio is ethylene carbonate: ethyl propionate: lithium hexafluoro phosphate: sub-
Sulfuric acid vinyl ester: 1,3- propane sultone=32.9%:50%:12%:0.1%:5%, the diaphragm are PE film；It is described
Cathode be artificial plumbago negative pole.
Embodiment 2
A kind of lithium ion battery that high temperature performance can combine, including anode, cathode, diaphragm, electrolyte, it is described just
Pole includes active material, conductive agent and binder, and the active material is the LiFePO of 800nm partial size4, conductive agent is graphite
Alkene, binder are polyacrylic acid, and the percentage that the active material, conductive agent, binder account for positive gross mass is respectively
99.4%:0.1%:0.5%；The electrolyte includes organic solvent, lithium salts, anode additive, cathode additive agent, described organic
Solvent is propene carbonate, methyl ethyl carbonate and ethyl propionate, and the lithium salts is bis- (trimethyl fluoride sulfonyl) imine lithiums and hexafluoro
Lithium phosphate, the anode additive are sulfuric acid vinyl ester, and the cathode additive agent is 1,3- propane sultone and ethylene carbonate
Ethyl, electrolyte composition ratio are propene carbonate: methyl ethyl carbonate: ethyl propionate: bis- (trimethyl fluoride sulfonyl) imine lithiums:
Lithium hexafluoro phosphate: sulfuric acid vinyl ester: 1,3- propane sultone: vinylethylene carbonate=23%:20%:25%:12%:
13%:5%:1%:1%, the diaphragm are PE film；The cathode is hard carbon cathode.
Embodiment 3
A kind of lithium ion battery that high temperature performance can combine, including anode, cathode, diaphragm, electrolyte, it is described just
Pole includes active material, conductive agent and binder.Active material is the LiFePO of 500nm partial size4, conductive agent be carbon nanotube and
Acetylene black, binder LA133, LiFePO4, carbon nanotube, acetylene black, LA133 ratio be 97%:0.5%:0.5%:2%；
The electrolyte includes organic solvent, lithium salts, anode additive, cathode additive agent, and the organic solvent is ethylene carbonate, carbon
Dimethyl phthalate, lithium salts are lithium hexafluoro phosphate, and anode additive is three (trimethyl silane) borates, cathode additive agent 1,3- third
Alkene sultones, electrolyte composition ratio are ethylene carbonate: dimethyl carbonate: lithium hexafluoro phosphate: three (trimethyl silane) boron
Acid esters: 1,3- propene sultone=32.9%:50%:15%:2%:0.1%, the diaphragm are PE film, and the cathode is behaved
Make graphite.
Comparative example 1
The preparation method of the lithium ion battery of this comparative example is same as Example 1, the difference is that active material is 2 μm
The LiFePO of partial size4。
Comparative example 2
The preparation method of the lithium ion battery of this comparative example is same as Example 2, the difference is that active material is 2 μm
The LiFePO of partial size4。
Comparative example 3
The preparation method of the lithium ion battery of this comparative example is same as Example 3, the difference is that active material is 3 μm
The LiFePO of partial size4。
Comparative example 4
The preparation method of the lithium ion battery of this comparative example is same as Example 1, the difference is that not adding positive addition
Agent ethylene sulfite, the ethyl propionate of addition account for the 50.1% of electrolyte.
Comparative example 5
The preparation method of the lithium ion battery of this comparative example is same as Example 2, the difference is that not adding positive addition
Agent sulfuric acid vinyl ester, the methyl ethyl carbonate of addition account for the 25% of electrolyte.
Comparative example 6
The preparation method of the lithium ion battery of this comparative example is same as Example 3, the difference is that not adding positive addition
Agent three (trimethyl silane) borate, the dimethyl carbonate of addition account for the 52% of electrolyte.
The application experiment of embodiment and comparative example:
55 DEG C of loop tests: in order to measure the battery high-temperature behavior using lithium ion produced by the present invention, following behaviour is carried out
Make: battery is placed in 55 DEG C, and with 2.2~3.65V, charge and discharge cycles are tested under 1C multiplying power.
Low temperature discharge test: in order to measure the battery cryogenic property using lithium ion produced by the present invention, following behaviour is carried out
Make: the fully charged battery of room temperature is placed at -30 DEG C after 4h with 10C multiplying power discharging 30 seconds.The high temperature of 1 embodiment and comparative example of table
Cycle performance and low temperature discharge test result:
As can be seen from Table 1, high when positive active material partial size is less than 1 μm, and after the specific anode additive of addition
Warm cyclical stability and low temperature performance obtain apparent advantageous effects, and the present invention uses LiFePO of the partial size less than 1 μm4With
The lithium ion battery of specific anode additive combination preparation has performance advantage outstanding, is mainly manifested in the height for promoting battery
Warm circulation volume conservation rate and promotion battery low temp power characteristic.Embodiment 1-3 is substantially better than its comparative example.
Therefore application lithium ion battery of the invention has high cryogenic property and durability, has high market
Value and social benefit.It is illustrating for possible embodiments of the invention above, but guarantor of the invention can not be limited
Protect range.
Claims (10)
1. the lithium ion battery that a kind of high temperature performance can combine, including anode, cathode, diaphragm and electrolyte, feature
Be: the anode includes active material, binder and conductive agent.
2. the lithium ion battery that a kind of high temperature performance according to claim 1 can combine, it is characterised in that: described
Active material accounts for the 95%~99.4% of positive gross mass, and the active material is LiFePO4, the LiFePO4The diameter of particle
Less than 1 μm.
3. the lithium ion battery that a kind of high temperature performance according to claim 1 can combine, it is characterised in that: described
Binder accounts for the 0.5%~3% of positive gross mass, the binder be in Kynoar, LA133 and polyacrylic acid at least
It is a kind of.
4. the lithium ion battery that a kind of high temperature performance according to claim 1 can combine, it is characterised in that: described
Conductive agent accounts for the 0.1%~2% of positive gross mass, and the conductive agent is carbon nanotube, graphene, at least one in acetylene black
Kind.
5. the lithium ion battery that a kind of high temperature performance according to claim 1 can combine, it is characterised in that: described
Electrolyte includes organic solvent, lithium salts, anode additive and cathode additive agent.
6. the lithium ion battery that a kind of high temperature performance according to claim 5 can combine, it is characterised in that: described
Organic solvent accounts for the 65%~87.8% of electrolyte gross mass, and the lithium salts accounts for the 12%~25% of electrolyte gross mass, described
Anode additive accounts for the 0.1%~5% of electrolyte gross mass, the cathode additive agent account for electrolyte gross mass 0.1%~
5%.
7. the lithium ion battery that a kind of high temperature performance according to claim 5 can combine, it is characterised in that: described
Organic solvent includes cyclic solvent and linear solvents, and the mass ratio of the cyclic solvent and linear solvents is 1~2:3.
8. the lithium ion battery that a kind of high temperature performance according to claim 7 can combine, it is characterised in that: described
Cyclic solvent be one of ethylene carbonate, propene carbonate, fluorinated ethylene carbonate, gamma-butyrolacton and gamma-valerolactone or
Multiple combinations；The linear solvents are dimethyl carbonate, in methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propionate
One or more combinations.
9. the lithium ion battery that a kind of high temperature performance according to claim 5 can combine, it is characterised in that: described
Lithium salts is lithium hexafluoro phosphate, double fluorine sulfimide lithiums, difluorine oxalic acid boracic acid lithium, bis- (trimethyl fluoride sulfonyl) imine lithiums and double oxalic acid
One of lithium borate or a variety of combinations.
10. the lithium ion battery that a kind of high temperature performance according to claim 5 can combine, it is characterised in that: institute
Stating anode additive is one of ethylene sulfite, sulfuric acid vinyl ester, three (trimethyl silane) borates or a variety of groups
It closes, the cathode additive agent is 1,3- propene sultone, 1,3- propane sultone, vinylethylene carbonate, sulfurous acid second
At least one of the double oxalic acid lithium phosphates of alkene ethyl, difluorophosphate, difluoro, tetrafluoro oxalic acid lithium phosphate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111640987A (en) * | 2020-06-11 | 2020-09-08 | 珠海冠宇电池股份有限公司 | High-power electrolyte and lithium ion battery containing same |
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Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai Guanyu Battery Co., Ltd. Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: Zhuhai Coslight Battery Co., Ltd. |
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Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai Guanyu Battery Co., Ltd Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
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