CN106299474A - Lithium titanate battery electrolyte and battery goods thereof - Google Patents
Lithium titanate battery electrolyte and battery goods thereof Download PDFInfo
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- CN106299474A CN106299474A CN201610833939.5A CN201610833939A CN106299474A CN 106299474 A CN106299474 A CN 106299474A CN 201610833939 A CN201610833939 A CN 201610833939A CN 106299474 A CN106299474 A CN 106299474A
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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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- 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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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium titanate battery electrolyte and battery goods thereof, it is mixed by solute, solvent and additive, described additive is alkyl phosphoric acid acid anhydride, and this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 0.1～10%；The present invention provides the formula of lithium titanate battery electrolyte to design ingenious, rationally add alkyl phosphoric acid acid anhydride, and its content of Scientific Establishment, can react with the water of lithium titanate pole piece and consume moisture, and the alkyl phosphoric acid acidity produced is low, will not destroy the both positive and negative polarity of battery, thus decrease gas production, significantly reduce expansion during high temperature storage, improve lithium titanate battery high-temperature cycle life, there is preferably high-temperature storage performance and cycle performance；The simple in construction of the battery goods that the above-mentioned lithium titanate battery electrolyte of application that the present invention provides prepares, it is easy to accomplish, there is preferably high-temperature storage performance and cycle performance, good combination property, beneficially wide popularization and application.
Description
Technical field
The invention belongs to lithium titanate battery technical field, be specifically related to a kind of lithium titanate battery electrolyte and battery system thereof
Product.
Background technology
Lithium rechargeable battery has higher running voltage relative to lead-acid accumulator, nickel-cadmium cell, Ni-MH battery, follows
Ring life-span and specific energy, it is thus achieved that be widely applied.Relative to graphite cathode, lithium titanate anode have longer cycle life,
Low temperature, big multiplying power and safety.Major embodiment is as follows:
1, lithium titanate is a kind of zero strain material, changes hardly with volume when completely putting completely filling, has longer circulation
Life-span.
2, lithium titanate is about 1.55V relative to the current potential of lithium, much larger than analysis lithium current potential, thus without graphite occur due to analysis
The safety problem that lithium causes.
3, owing to not having SEI film to generate, lithium titanate battery has higher efficiency first.
4, lithium titanate has a higher lithium ion diffusion coefficient relative to graphite, thus have more preferable cryogenic property and times
Rate performance.
But, lithium titanate battery has the disadvantage that battery easy flatulence in high temperature storage and cyclic process, have impact on
The circulation of battery and security performance.Its reason have following some: 1. lithium titanate specific surface area is big, easily absorbs water；2. lithium titanate can
Can be with water of crystallization, even if high-temperature baking also is difficult to remove；3. the tetravalence of lithium titanate has strong catalysis activity, electrolyte
Solvent is easy on lithium titanate surface reduction reaction, especially reacts when high temperature and becomes apparent from.
Summary of the invention
For above-mentioned deficiency, one of the object of the invention is, it is provided that a kind of formula is reasonable, it is possible to suppression lithium titanate battery
Aerogenesis, is effectively improved the high temperature storage of lithium titanate battery and the lithium titanate battery electrolyte of cycle performance.
The two of the object of the invention are, it is provided that a kind of battery goods applying above-mentioned lithium titanate battery electrolyte to prepare,
These battery goods have preferably high-temperature storage performance and cycle performance.
For achieving the above object, technical scheme provided by the present invention is:
A kind of lithium titanate battery electrolyte, it mixes by solute, solvent and additive, and described additive is alkyl phosphoric acid
Acid anhydride, the structural formula of this alkyl phosphoric acid acid anhydride is as follows:
Wherein alkyl R is the alkyl of C1-C5, and this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is
0.1～10%.Research finds that the size of water content has vital impact to the gas production of lithium titanate battery, works as water content
When increasing, gas production can the increase drastically along with the increase of water content.Therefore, if lithium titanate can be reduced by electrolyte bear
The water content of pole piece, will can significantly improve high temperature storage and the cycle performance of lithium titanate battery.When additive alkyl phosphoric acid acid anhydride contains
When amount is less than 0.1%, the amount of additive is not enough to all remove moisture therein, improves not clear to circulating battery and high-temperature behavior
Aobvious；When additive alkyl phosphoric acid acid anhydride content is more than 10%, electrolyte viscosity becomes big, the multiplying power of battery and deteriorated low temperature performance.
Therefore the mass content scope of suitable alkyl phosphoric acid acid anhydride is 0.1～10%.
As a modification of the present invention, described alkyl phosphoric acid acid anhydride percent mass in lithium titanate battery electrolyte contains
Amount is 0.2～7%.
As a modification of the present invention, described alkyl phosphoric acid acid anhydride percent mass in lithium titanate battery electrolyte contains
Amount is 0.3～5%.
As a modification of the present invention, described solvent is ethylene carbonate, Allyl carbonate, dimethyl carbonate, carbonic acid
Diethylester, Ethyl methyl carbonate, methyl propyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, third
The combination of one or more in propyl propionate, methyl butyrate, ethyl n-butyrate., gamma-butyrolacton, acetonitrile, oxolane.
As a modification of the present invention, described solute be lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, two
Fluorine Lithium bis (oxalate) borate, lithium perchlorate, double (trimethyl fluoride sulfonyl) imine lithium, double (fluorine sulphonyl) imine lithium, lithium carbonate, lithium fluoride,
One or more combinations in lithium perchlorate.
The battery goods that in a kind of application, described lithium titanate battery electrolyte prepares, it includes outer package, is positioned at outsourcing
Battery core in dress, this battery core includes positive and negative electrode assembly and the isolating membrane between positive and negative electrode assembly, note in described outer package
Enter to have the right in requirement 1-5 the lithium titanate battery electrolyte described in any one, and described positive electrode includes positive pole and positive pole
Active substance, described negative pole assembly includes that negative pole and negative electrode active material, wherein said negative electrode active material are lithium titanate.
As a modification of the present invention, described positive active material is LiMn2O4, cobalt acid lithium or manganese nickel cobalt ternary material.
As a modification of the present invention, described positive active material is that manganese nickel cobalt ternary mixes LiMn2O4.
As a modification of the present invention, described positive active material is LiNi0.33Co0.33Mn0.33O2Mixed LiMn2O4.
The invention have the benefit that the present invention provides the formula of lithium titanate battery electrolyte to design ingenious, rationally add
Enter alkyl phosphoric acid acid anhydride, and its content of Scientific Establishment, it is possible to react with the water of lithium titanate pole piece and consume moisture, and the alkyl produced
Phosphoric acid acid is low, will not destroy the both positive and negative polarity of battery, thus decrease gas production, swollen when significantly reducing high temperature storage
Swollen, improve lithium titanate battery high-temperature cycle life, there is preferably high-temperature storage performance and cycle performance；The present invention provides
Apply the simple in construction of battery goods that above-mentioned lithium titanate battery electrolyte prepares, it is easy to accomplish, have the highest gentle
Storage performance and cycle performance, good combination property, beneficially wide popularization and application.
Below in conjunction with embodiment, the invention will be further described.
Detailed description of the invention
Embodiment 1: a kind of lithium titanate battery electrolyte that the present embodiment provides, it is mixed by solute, solvent and additive
Conjunction forms, and described additive is alkyl phosphoric acid acid anhydride, and the structural formula of this alkyl phosphoric acid acid anhydride is as follows:
Wherein alkyl R is the alkyl of C1-C5, and this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is
0.1%.
It is also preferred that the left described solvent is ethylene carbonate (EC), Allyl carbonate (PC), dimethyl carbonate (DMC), carbonic acid two
Ethyl ester (DEC), Ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), methyl acetate (MA), ethyl acetate (EA), propyl acetate
(PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl n-butyrate. (EB), γ-Ding Nei
The combination of one or more in ester (GBL), acetonitrile (CH3CN), oxolane (THF).
Described solute be lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, lithium perchlorate,
One or more in double (trimethyl fluoride sulfonyl) imine lithium, double (fluorine sulphonyl) imine lithium, lithium carbonate, lithium fluoride, lithium perchlorate
Combination.
The battery goods that in a kind of application, described lithium titanate battery electrolyte prepares, it includes outer package, is positioned at outsourcing
Battery core in dress, this battery core includes positive and negative electrode assembly and the isolating membrane between positive and negative electrode assembly, note in described outer package
Enter to have the right in requirement 1-5 the lithium titanate battery electrolyte described in any one, and described positive electrode includes positive pole and positive pole
Active substance, described negative pole assembly includes that negative pole and negative electrode active material, wherein said negative electrode active material are lithium titanate.
In the present embodiment, described positive active material is LiMn2O4, cobalt acid lithium or manganese nickel cobalt ternary material.Other embodiments
In, this positive active material can also mix LiMn2O4 or LiNi for manganese nickel cobalt ternary0.33Co0.33Mn0.33O2Mixed LiMn2O4.
The simple in construction of the battery goods that the above-mentioned lithium titanate battery electrolyte of application that the present invention provides prepares, it is easy to real
Existing, there is preferably high-temperature storage performance and cycle performance, good combination property.
Embodiment 2: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 0.2%.
Embodiment 3: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 0.3%.
Embodiment 4: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 0.3%.
Embodiment 5: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 0.3%.
Embodiment 6: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 1%.
Embodiment 7: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 4%.
Embodiment 8: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 5%.
Embodiment 9: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 6%.
Embodiment 10: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 7%.
Embodiment 11: a kind of lithium titanate battery electrolyte of the present embodiment offer and battery goods thereof, itself and embodiment 1
Essentially identical, difference is that this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is 10%.
Above-described embodiment is only the preferable embodiment of the present invention, and the present invention can not enumerate out whole embodiment party
Formula, the technical scheme of one of all employing above-described embodiments, or the equivalent variations done according to above-described embodiment, all protect in the present invention
In the range of protecting.Several groups of alkyl phosphoric acid acid anhydrides of random choose weight/mass percentage composition data pair in lithium titanate battery electrolyte below
The present invention further illustrates.
Embodiment 12:
By stirring material, coating, pole piece are colded pressing, wind, encapsulate, toast moisture removal obtains treating the battery core of fluid injection, wherein positive-active
Material is that ternary mixes LiMn2O4 (LiNi0.33Co0.33Mn0.33O2/ LMO=50/50), negative electrode active material is lithium titanate, lithium titanate
Battery electrolytic solution is 1mol/L LiPF6/ (PC/DEC=35: 65)+0.3% 1-propylphosphonic anhydride (PPACA), soft-package battery
Model be 523450 (thickness be 5.2mm, width 34mm, length 50mm).Battery core is completely charged to 2.8V, is then put in 80 DEG C
Baking oven in place 6 hours, its hot Thickness Measurement by Microwave expansion rate is 29%, and cold Thickness Measurement by Microwave expansion rate is 13%, and capability retention is 85%,
Capacity restoration rate is 89%.In storing at 60 DEG C/7 days, its hot Thickness Measurement by Microwave expansion rate is 34%, and cold Thickness Measurement by Microwave expansion rate is 22%,
Capability retention is 86%, and capacity restoration rate is 92%.
The electrolyte organized as a comparison does not add the battery of 1-propylphosphonic anhydride (PPACA), puts in the baking oven of 80 DEG C
After putting 6 hours, its hot Thickness Measurement by Microwave expansion rate is 47%, and cold Thickness Measurement by Microwave expansion rate is 18%, and capability retention is 82%, capacity restoration
Rate is 87%.Placing after heat Thickness Measurement by Microwave expansion rate at 60 DEG C/7 days is 50%, and cold Thickness Measurement by Microwave expansion rate is 29%, and capability retention is
82%, capacity restoration rate is 87%.
Shown by above-mentioned data, after adding the 1-propylphosphonic anhydride (PPACA) of 0.3%, can help to suppress battery core
High-temperature expansion, the capacity improving battery core keeps and recovery rate.High rate performance: during 10C, capability retention is 87%, holds during 15C
Amount conservation rate is 68%.
And contrast groups when being 10C capability retention be 86%, during 15C, capability retention is 67%.
In the charge and discharge of room temperature 5C circulates, 1000 weeks capacity of electrolyte of the 1-propylphosphonic anhydride (PPACA) having added 0.3% are protected
Holdup is 98%；In 45 degree of 5C charge and discharge circulations, within 1000 weeks, reach 88%；
And contrast groups room temperature 5C charge and discharge circulates 1000 weeks and can reach 92%, 45 degree of circulations can reach 82%.To sum up, the 1-of 0.3%
Propylphosphonic anhydride (PPACA) significantly improves high temperature storage and the cycle performance of lithium titanate battery.
Embodiment 13:
By stirring material, coating, pole piece are colded pressing, wind, encapsulate, toast moisture removal obtains treating the battery core of fluid injection, wherein positive-active
Material is that ternary mixes LiMn2O4 (LiNi0.33Co0.33Mn0.33O2/ LMO=50/50), negative electrode active material is lithium titanate, lithium titanate
Battery electrolytic solution is 1mol/L LiPF6/ (PC/DEC=35: 65)+1% 1-propylphosphonic anhydride (PPACA), soft-package battery
Model be 523450 (thickness be 5.2mm, width 34mm, length 50mm).Battery core is completely charged to 2.8V, is then put in 80 DEG C
Placing 6 hours in baking oven, its hot Thickness Measurement by Microwave expansion rate is 30%, and cold Thickness Measurement by Microwave expansion rate is 12%, and capability retention is 86.5%,
Capacity restoration rate is 89%.In storing at 60 DEG C/7 days, its hot Thickness Measurement by Microwave expansion rate is 30%, and cold Thickness Measurement by Microwave expansion rate is 19%,
Capability retention is 87.5%, and capacity restoration rate is 93%.
The electrolyte organized as a comparison does not add 1-propylphosphonic anhydride (PPACA), places 6 hours in the baking oven of 80 DEG C
After, its hot Thickness Measurement by Microwave expansion rate is 47%, and cold Thickness Measurement by Microwave expansion rate is 18%, and capability retention is 82%, and capacity restoration rate is
87%.Placing after heat Thickness Measurement by Microwave expansion rate at 60 DEG C/7 days is 50%, and cold Thickness Measurement by Microwave expansion rate is 29%, and capability retention is 82%,
Capacity restoration rate is 87%.
Shown by above-mentioned data, after adding the 1-propylphosphonic anhydride (PPACA) of 1%, can help to suppress the height of battery core
Temperature expands, and the capacity improving battery core keeps and recovery rate.High rate performance: during 10C, capability retention is 87%, capacity during 15C
Conservation rate is 76%.And contrast groups when being 10C capability retention be 86%, during 15C, capability retention is 67%.
In the charge and discharge of room temperature 5C circulates, 1000 weeks capacity of electrolyte of the 1-propylphosphonic anhydride (PPACA) having added 1% keep
Rate is 99%；In 45 degree of 5C charge and discharge circulations, within 1000 weeks, reach 90%；And contrast groups room temperature 5C charge and discharge circulates 1000 weeks and can reach
92%, 45 degree of circulations can reach 82%.To sum up, the 1-propylphosphonic anhydride (PPACA) of 1% significantly improves the height of lithium titanate battery
Gentle storage and cycle performance.
Embodiment 13:
By stirring material, coating, pole piece are colded pressing, wind, encapsulate, toast moisture removal obtains treating the battery core of fluid injection, wherein positive-active
Material is that ternary mixes LiMn2O4 (LiNi0.33Co0.33Mn0.33O2/ LMO=50/50), negative electrode active material is lithium titanate, lithium titanate
Battery electrolytic solution is 1mol/L LiPF6/ (PC/DEC=35: 65)+5% 1-propylphosphonic anhydride (PPACA), soft-package battery
Model be 523450 (thickness be 5.2mm, width 34mm, length 50mm).Battery core is completely charged to 2.8V, is then put in 80 DEG C
Placing 6 hours in baking oven, its hot Thickness Measurement by Microwave expansion rate is 33%, and cold Thickness Measurement by Microwave expansion rate is 11%, and capability retention is 87%, holds
Amount recovery rate is 90%.In storing at 60 DEG C/7 days, its hot Thickness Measurement by Microwave expansion rate is 26%, and cold Thickness Measurement by Microwave expansion rate is 16%, holds
Amount conservation rate is 88%, and capacity restoration rate is 94%.
The electrolyte organized as a comparison does not add the battery of 1-propylphosphonic anhydride (PPACA), puts in the baking oven of 80 DEG C
After putting 6 hours, its hot Thickness Measurement by Microwave expansion rate is 47%, and cold Thickness Measurement by Microwave expansion rate is 18%, and capability retention is 82%, capacity restoration
Rate is 87%.Placing after heat Thickness Measurement by Microwave expansion rate at 60 DEG C/7 days is 50%, and cold Thickness Measurement by Microwave expansion rate is 29%, and capability retention is
82%, capacity restoration rate is 87%.
Shown by above-mentioned data, after adding the 1-propylphosphonic anhydride (PPACA) of 5%, can help to suppress the height of battery core
Temperature expands, and the capacity improving battery core keeps and recovery rate.High rate performance: during 10C, capability retention is 82%, capacity during 15C
Conservation rate is 60%.And contrast groups when being 10C capability retention be 86%, during 15C, capability retention is 67%.
In the charge and discharge of room temperature 5C circulates, 1000 weeks capacity of electrolyte of the 1-propylphosphonic anhydride (PPACA) having added 5% keep
Rate is 99%；In 45 degree of 5C charge and discharge circulations, within 1000 weeks, reach 90%；And contrast groups room temperature 5C charge and discharge circulates 1000 weeks and can reach
92%, 45 degree of circulations can reach 82%.To sum up, the 1-propylphosphonic anhydride (PPACA) of 5% significantly improves the height of lithium titanate battery
Gentle storage and cycle performance.
Embodiment 14:
By stirring material, coating, pole piece are colded pressing, wind, encapsulate, toast moisture removal obtains treating the battery core of fluid injection, wherein positive-active
Material is that ternary mixes LiMn2O4 (LiNi0.33Co0.33Mn0.33O2/ LMO=50/50), negative electrode active material is lithium titanate, lithium titanate
Battery electrolytic solution is 1mol/L LiPF6/ (PC/DEC=35: 65)+1% methyl acid phosphate acid anhydride (MPA), the model of soft-package battery
Be 523450 (thickness be 5.2mm, width 34mm, length 50mm).Battery core is completely charged to 2.8V, is then put in the baking oven of 80 DEG C
Middle placement 6 hours, its hot Thickness Measurement by Microwave expansion rate is 32%, and cold Thickness Measurement by Microwave expansion rate is 14%, and capability retention is 85%, and capacity is extensive
Multiple rate is 88%.In storing at 60 DEG C/7 days, its hot Thickness Measurement by Microwave expansion rate is 26%, and cold Thickness Measurement by Microwave expansion rate is 16%, and capacity is protected
Holdup is 88%, and capacity restoration rate is 94%.
The electrolyte organized as a comparison does not add the battery of methyl acid phosphate acid anhydride (MPA), places 6 little in the baking oven of 80 DEG C
Shi Hou, its hot Thickness Measurement by Microwave expansion rate is 47%, and cold Thickness Measurement by Microwave expansion rate is 18%, and capability retention is 82%, and capacity restoration rate is
87%.Placing after heat Thickness Measurement by Microwave expansion rate at 60 DEG C/7 days is 50%, and cold Thickness Measurement by Microwave expansion rate is 29%, and capability retention is 82%,
Capacity restoration rate is 87%.
Being shown by above-mentioned data, after adding the methyl acid phosphate acid anhydride (MPA) of 1%, the high temperature that can help to suppress battery core is swollen
Swollen, the capacity improving battery core keeps and recovery rate.High rate performance: during 10C, capability retention is 86%, during 15C, capacity keeps
Rate is 72%.And contrast groups when being 10C capability retention be 86%, during 15C, capability retention is 67%.
In the charge and discharge of room temperature 5C circulates, 1000 weeks capability retentions of electrolyte of the methyl acid phosphate acid anhydride (MPA) having added 1% exist
98%；In 45 degree of 5C charge and discharge circulations, within 1000 weeks, reach 87%；And contrast groups room temperature 5C charge and discharge circulates 1000 weeks and can reach 92%, 45
Degree circulation can reach 82%.To sum up, the methyl acid phosphate acid anhydride (MPA) of 1% can significantly improve lithium titanate battery high temperature storage and
Cycle performance.
In sum, containing 0.1～the alkyl phosphoric acid acid anhydride of 10% in lithium titanate battery electrolyte of the present invention, can not only
Enough reduce battery core storing, especially thickness swelling during high temperature storage, and the cycle performance of battery core can be significantly improved, to electricity
The high rate performance in pond does not has much affect yet.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula changes and revises.Therefore, the invention is not limited in detailed description of the invention disclosed and described above, to the present invention's
Some modifications and changes should also be as falling in the scope of the claims of the present invention.Although additionally, this specification using
Some specific terms, but these terms are merely for convenience of description, the present invention does not constitute any restriction.Such as the present invention
Described in above-described embodiment, use same or similarity method and component and other electrolyte of obtaining and battery goods thereof, all
In scope.
Claims (9)
1. a lithium titanate battery electrolyte, it is mixed by solute, solvent and additive, it is characterised in that described in add
Adding agent is alkyl phosphoric acid acid anhydride, and the structural formula of this alkyl phosphoric acid acid anhydride is as follows:
Wherein alkyl R is the alkyl of C1-C5, and this alkyl phosphoric acid acid anhydride weight/mass percentage composition in lithium titanate battery electrolyte is
0.1～10%.
Lithium titanate battery electrolyte the most according to claim 1, it is characterised in that described alkyl phosphoric acid acid anhydride is at lithium titanate
Weight/mass percentage composition in battery electrolytic solution is 0.2～7%.
Lithium titanate battery electrolyte the most according to claim 1, it is characterised in that described alkyl phosphoric acid acid anhydride is at lithium titanate
Weight/mass percentage composition in battery electrolytic solution is 0.3～5%.
4. according to the lithium titanate battery electrolyte described in claim 1-3 any one, it is characterised in that described solvent is carbon
Vinyl acetate, Allyl carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, methyl acetate, acetic acid
Ethyl ester, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl n-butyrate., gamma-butyrolacton, acetonitrile, four
The combination of one or more in hydrogen furan.
5. according to the lithium titanate battery electrolyte described in claim 1 any one, it is characterised in that described solute is hexafluoro
Lithium phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, lithium perchlorate, double (trimethyl fluoride sulfonyl) imines
One or more combinations in lithium, double (fluorine sulphonyl) imine lithium, lithium carbonate, lithium fluoride, lithium perchlorate.
6. applying the battery goods that in claim 1-5, lithium titanate battery electrolyte described in any one prepares, it is special
Levying and be, it includes outer package, is positioned at the battery core of outer package, and this battery core includes positive and negative electrode assembly and between positive and negative electrode assembly
Between isolating membrane, be injected with the lithium titanate battery electrolyte described in any one in claim 1-5 in described outer package,
Described positive electrode includes that positive pole and positive active material, described negative pole assembly include negative pole and negative electrode active material, Qi Zhongsuo
The negative electrode active material stated is lithium titanate.
Battery goods the most according to claim 6, it is characterised in that described positive active material is LiMn2O4, cobalt acid lithium
Or manganese nickel cobalt ternary material.
Battery goods the most according to claim 6, it is characterised in that described positive active material is that manganese nickel cobalt ternary mixes manganese
Acid lithium.
Battery goods the most according to claim 6, it is characterised in that described positive active material is
LiNi0.33Co0.33Mn0.33O2Mixed LiMn2O4.
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| CN201610833939.5A CN106299474A (en) | 2016-09-20 | 2016-09-20 | Lithium titanate battery electrolyte and battery goods thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109687021A (en) * | 2018-12-18 | 2019-04-26 | 东莞市杉杉电池材料有限公司 | A kind of high temp resistance lithium ion cell nonaqueous electrolytic solution |
| CN114006125A (en) * | 2021-10-29 | 2022-02-01 | 河北金力新能源科技股份有限公司 | High-temperature-storage-resistant oil-based lithium ion battery diaphragm and preparation method thereof |
| EP3754775A4 (en) * | 2018-02-16 | 2022-03-16 | Daikin Industries, Ltd. | Electrolysis solution, electrochemical device, lithium-ion secondary battery, and module |
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| CN107293786A (en) * | 2017-06-21 | 2017-10-24 | 颍上北方动力新能源有限公司 | A kind of formula of lithium battery electrolytes and preparation method thereof |
| EP3754775A4 (en) * | 2018-02-16 | 2022-03-16 | Daikin Industries, Ltd. | Electrolysis solution, electrochemical device, lithium-ion secondary battery, and module |
| CN109687021A (en) * | 2018-12-18 | 2019-04-26 | 东莞市杉杉电池材料有限公司 | A kind of high temp resistance lithium ion cell nonaqueous electrolytic solution |
| CN114006125A (en) * | 2021-10-29 | 2022-02-01 | 河北金力新能源科技股份有限公司 | High-temperature-storage-resistant oil-based lithium ion battery diaphragm and preparation method thereof |
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