CN110504489A - A kind of 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes - Google Patents
A kind of 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes Download PDFInfo
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- CN110504489A CN110504489A CN201910741716.XA CN201910741716A CN110504489A CN 110504489 A CN110504489 A CN 110504489A CN 201910741716 A CN201910741716 A CN 201910741716A CN 110504489 A CN110504489 A CN 110504489A
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- lithium
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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
- 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
- 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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Abstract
The invention belongs to lithium-ion battery electrolytes preparation technical fields, and in particular to a kind of 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes.The electrolyte is made of electrolyte lithium salt, non-aqueous organic solvent, cathode film formation additive and positive film for additive.Lithium-ion battery electrolytes prepared by the present invention can be obviously improved dissolved out under high temperature and pressure in nickel lithium manganate cathode material because of metal ion caused by cycle performance of battery the problem of declining rapidly, make battery that there is excellent circulation ability and coulombic efficiency.
Description
Technical field
The invention belongs to lithium-ion battery electrolytes preparation technical fields, and in particular to a kind of 5V high-voltage lithium nickel manganate is just
Pole lithium-ion battery electrolytes.
Background technique
Lithium ion battery has many advantages, such as energy density is big, charge-discharge performance is stable, long service life, is small data
One of the main candidate electrical source of power of code and large-sized power plant.Lithium ion battery improve energy density method first is that improve
The operating voltage of battery.Researchers develop many high voltage bearing positive electrodes, including rich lithium material, Transition metal substituted point
Spinel, spinel nickel LiMn2O4 etc..In many positive electrodes, spinel nickel LiMn2O4 LiN0.5Mn1.5O4Because of tool
There is higher operating voltage (4.95 V vs. Li/Li of upper voltage limit+) and height ratio capacity (147mAh/g) and by more and more
The concern of professional.
However, the solvent master carbonate solvent to be used of traditional electrolyte, and carbonate solvent is greater than 4.5V in voltage
Under the conditions of can positive electrode can persistently dissolve out due to transition metal ions so that positive by continued oxidation, and under high voltage condition
Structure is constantly destroyed, and battery is caused to have lower coulombic efficiency and poor cycle life.
In order to overcome the above problem, researchers propose many effective solution sides from material modification technology
Case, so that cycle life significantly improves under high pressure.Application publication number CN106099084A, date of publication 2016.11.09
Patent of invention disclose a kind of surface cladding type nickel ion doped material, lithium battery and preparation method thereof, which passes through in L i
N i 0 .5 M n 1 .5 O 4Surface coats the LiM of one layer of spinel structure0 .5Mn1 .5O4, wherein M is positive bivalent metal ion.
The material particle size of the invention is small and uniform, is conducive to improve LiNi0 .5Mn1 .5O4Chemical property.Above-mentioned patent changes from material
Property angle is set out, and the operational sequence in material preparation process is increased, so that preparing cumbersome, is unfavorable for large-scale production.
Summary of the invention
It is electrolysed in view of this, the purpose of the present invention is to provide a kind of 5V high-voltage lithium nickel manganate anodes with lithium ion battery
Liquid, by adding functional form additive in the electrolytic solution, forms positive-pole protective layer in positive electrode surface from electrolyte angle
Stablize the anode structure under high voltage condition, which passes through the adjustment of additive, final to realize that blanking voltage reach
4.95V。
The technical scheme adopted by the invention is as follows:
A kind of 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes, the electrolyte is by electrolyte lithium salt, non-aqueous organic
Solvent, cathode film formation additive and positive film for additive composition；
The anode film for additive is aminoamide class compound；
The cathode film formation additive is at least one in fluoro ethylene carbonate (FEC) and ethylene carbonate Asia ethylene rouge (VEC)
Kind.
Further preferably, in the electrolyte, the concentration of electrolyte lithium salt is 1.0-1.2M, the matter of cathode film formation additive
Amount concentration is 1-5%, and the mass concentration of positive film for additive is 0.5-3%.
Further preferably, the non-aqueous organic solvent is ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate
(DMC), diethyl carbonate (DEC), methyl ethyl carbonate rouge (EMC), γ-fourth lactones (GBL), ethyl acetate (EA), ethyl propionate
(EP), butyric acid formicester (MB), the third rouge of propionic acid (PP), two or more in methyl acetate (MA).
Specifically, the structural formula of the aminoamide class compound is as follows:
R1~R2For CH3、C2H5、C3H7、C4H9、CF3、CF3CH2、CF2HCH2、CF3CF2、CF2HCF2CH2、CF3CFHCF2、
CF3CF2CH2、CF3CF2CF2、(CF3)2CH、(CF3)3C、CF3CF2CF2CF2、OCH2CF3、OCH(CF3)2It is any.
Further preferably, the non-aqueous organic solvent is diethyl carbonate (DEC), methyl ethyl carbonate rouge (EMC) and carbonic acid second
Alkene rouge (EC) presses the mixture of 1:1:1 volume ratio.
Further preferably, the non-aqueous organic solvent is dimethyl carbonate (DMC), methyl ethyl carbonate rouge (EMC) and carbonic acid second
Alkene rouge (EC) presses the mixture of 4:3:3 volume ratio.
Specifically, the electrolyte lithium salt is lithium hexafluoro phosphate (LiPF6)。
The above 5V high-voltage lithium nickel manganate anode of the invention mixes each raw material when being prepared with lithium-ion battery electrolytes
.
Compared with prior art, the present invention has following technical advantage:
In raw material of the invention, selected be suitable for cathode film formation additive of the present invention and anode film for additive so that lithium from
The blanking voltage of sub- battery can reach 4.95V, especially the aminoamide class compound in the present invention, be applied to just extremely nickel mangaic acid
In the lithium ion battery of lithium, make battery that there is excellent circulation ability and coulombic efficiency.Using lithium-ion electric prepared by the present invention
Pond electrolyte can be obviously improved dissolved out under high temperature and pressure in nickel lithium manganate cathode material because of metal ion caused by circulating battery
The problem of performance declines rapidly.Process is simple when prepared by electrolyte of the invention, is suitble to large-scale production.
Specific embodiment
Illustrate a specific embodiment of the invention below with reference to embodiment, but following embodiment is used only to be described in detail
The present invention does not limit the scope of the invention in any way.
5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes, embodiment 1-6, concrete composition are as follows:
Comparative example: a kind of lithium-ion battery electrolytes, composition are as follows: the LiPF of 1.2 M concentration6 , 0.5% methane-disulfonic acid Asia
Methyl esters (MMDS), 5%FEC, the solvent (mixture that volume ratio is DEC, EMC and EC of 1:1:1) of surplus.Concrete operations are as follows:
Full of argon gas glove box (moisture < 1ppm, oxygen < 1ppm) in, by each material stirring it is uniform after obtain comparative example
Lithium-ion battery electrolytes (free acid < 15ppm, moisture < 10ppm) form.
The same comparative example of the preparation method of embodiment 1-6.
The electrolyte injection that embodiment 1-6 and comparative example are obtained is by sufficiently dry graphite/L iN i0 .5M
n1 .5O4Battery, battery is stood by an envelope, preliminary filling is melted into, it is normal that the .95V of 3.0V~4 1C cycle charge-discharge is carried out after two envelope partial volumes
Warm loop test and 4 .95V expire electricity 60 DEG C/7d of state storage test.
Normal temperature circulation test condition: under the conditions of 25 DEG C ± 3 DEG C, battery is charged in a manner of 1C multiplying power constant current-constant pressure
To 4 .95V, cut-off current is 0 .05C；Then with 1C constant-current discharge to 3 .0V, a 1C charge and discharge cycles are completed；In repetition
Charge and discharge process is stated, with the 300th discharge capacity divided by the discharge capacity of first time, circulation 300 times capacity is obtained and keeps
Rate.
60 DEG C of high-temperature storage test conditions: by battery with 0 .5C multiplying power constant-current constant-voltage charging to 4 .95V, it is thick to test battery
Battery, is then put into 60 DEG C of baking ovens, battery is taken out after 7 days, tests cell thickness while hot, be down to room to battery by degree, internal resistance
Internal resistance is tested after temperature.
Cell thickness before cell thickness bulging rate=(cell thickness before cell thickness-storage after storage)/storage.
Experimental result see the table below:
It can be seen that under 4.95V high voltage condition from above-mentioned test data, just extremely nickel ion doped, cathode are the electricity of graphite
Pond, comparative example adds 300 circulation volume conservation rates 70% or so after MMDS, and 1-6 of the embodiment of the present invention is added with aminoamide
The battery capacity conservation rate of class compound is 84% or more.And the product battery that electrolyte is made into embodiment 1-6 experienced
Its thickness change and internal resistance change rate are well below comparative example after 60 DEG C of 7 days high temperature are shelved.In conclusion the present invention mentions
For lithium ion battery high-voltage electrolyte, cycle performance of the lithium ion battery under high voltage condition can be greatly improved,
It is advantageously implemented the commercialization of nickel ion doped lithium ion battery.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, this field is common
Other modifications or equivalent replacement that technical staff makes technical solution of the present invention, without departing from technical solution of the present invention
Spirit and scope, be intended to be within the scope of the claims of the invention.
Claims (7)
1. a kind of 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes, it is characterised in that: the electrolyte is by electrolyte
Lithium salts, non-aqueous organic solvent, cathode film formation additive and positive film for additive composition；
The anode film for additive is aminoamide class compound；
The cathode film formation additive is at least one of fluoro ethylene carbonate and ethylene carbonate Asia ethylene rouge.
2. 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes according to claim 1, it is characterised in that: institute
It states in electrolyte, the concentration of electrolyte lithium salt is 1.0-1.2M, and the mass concentration of cathode film formation additive is 1-5%, anode film forming
The mass concentration of additive is 0.5-3%.
3. 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes according to claim 1 or 2, feature exist
In: the non-aqueous organic solvent be ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate rouge,
It is γ-fourth lactones, ethyl acetate, ethyl propionate, butyric acid formicester, the third rouge of propionic acid, two or more in methyl acetate.
4. 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes according to claim 1 or 2, feature exist
In: the structural formula of the aminoamide class compound is as follows:
R1~R2For CH3、C2H5、C3H7、C4H9、CF3、CF3CH2、CF2HCH2、CF3CF2、CF2HCF2CH2、CF3CFHCF2、
CF3CF2CH2、CF3CF2CF2、(CF3)2CH、(CF3)3C、CF3CF2CF2CF2、OCH2CF3、OCH(CF3)2It is any.
5. 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes according to claim 1 or 2, feature exist
In: the electrolyte lithium salt is lithium hexafluoro phosphate.
6. 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes according to claim 3, it is characterised in that: institute
Stating non-aqueous organic solvent is the mixture of diethyl carbonate, methyl ethyl carbonate rouge and ethylene carbonate by 1:1:1 volume ratio.
7. 5V high-voltage lithium nickel manganate anode lithium-ion battery electrolytes according to claim 3, it is characterised in that: institute
Stating non-aqueous organic solvent is the mixture of dimethyl carbonate, methyl ethyl carbonate rouge and ethylene carbonate by 4:3:3 volume ratio.
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| CN201910741716.XA CN110504489B (en) | 2019-08-12 | 2019-08-12 | Lithium ion battery electrolyte for 5V high-voltage lithium nickel manganese oxide positive electrode |
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| CN201910741716.XA CN110504489B (en) | 2019-08-12 | 2019-08-12 | Lithium ion battery electrolyte for 5V high-voltage lithium nickel manganese oxide positive electrode |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111293363A (en) * | 2020-04-07 | 2020-06-16 | 广西民族师范学院 | High-voltage lithium nickel manganese oxide lithium ion battery electrolyte and secondary battery containing same |
| CN111540953A (en) * | 2020-05-12 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Lithium ion battery high-voltage electrolyte for lithium nickel manganese oxide cathode material |
| CN115332637A (en) * | 2022-09-06 | 2022-11-11 | 香河昆仑新能源材料股份有限公司 | High lithium salt concentration electrolyte and use method thereof in lithium ion battery |
| CN117728034A (en) * | 2024-02-07 | 2024-03-19 | 新乡华锐锂电新能源股份有限公司 | Lithium ion battery electrolyte capable of being subjected to rate discharge at ultralow temperature and preparation method thereof |
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| US20040091772A1 (en) * | 2002-06-20 | 2004-05-13 | Boris Ravdel | Lithium-ion battery electrolytes with improved thermal stability |
| CN102593516A (en) * | 2012-03-30 | 2012-07-18 | 厦门大学 | Flame-retardant lithium ion battery electrolyte and method for preparing same |
| CN106565774A (en) * | 2016-10-27 | 2017-04-19 | 湖北沙隆达股份有限公司 | Continuous tower-type washing method of O,O-dimethylphosphoroamidothioate crude product |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040091772A1 (en) * | 2002-06-20 | 2004-05-13 | Boris Ravdel | Lithium-ion battery electrolytes with improved thermal stability |
| CN102593516A (en) * | 2012-03-30 | 2012-07-18 | 厦门大学 | Flame-retardant lithium ion battery electrolyte and method for preparing same |
| CN106565774A (en) * | 2016-10-27 | 2017-04-19 | 湖北沙隆达股份有限公司 | Continuous tower-type washing method of O,O-dimethylphosphoroamidothioate crude product |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111293363A (en) * | 2020-04-07 | 2020-06-16 | 广西民族师范学院 | High-voltage lithium nickel manganese oxide lithium ion battery electrolyte and secondary battery containing same |
| CN111293363B (en) * | 2020-04-07 | 2022-08-26 | 广西民族师范学院 | High-voltage lithium nickel manganese oxide lithium ion battery electrolyte and secondary battery containing same |
| CN111540953A (en) * | 2020-05-12 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Lithium ion battery high-voltage electrolyte for lithium nickel manganese oxide cathode material |
| CN115332637A (en) * | 2022-09-06 | 2022-11-11 | 香河昆仑新能源材料股份有限公司 | High lithium salt concentration electrolyte and use method thereof in lithium ion battery |
| CN115332637B (en) * | 2022-09-06 | 2024-03-26 | 香河昆仑新能源材料股份有限公司 | High-lithium-salt-concentration electrolyte and application method thereof in lithium ion battery |
| CN117728034A (en) * | 2024-02-07 | 2024-03-19 | 新乡华锐锂电新能源股份有限公司 | Lithium ion battery electrolyte capable of being subjected to rate discharge at ultralow temperature and preparation method thereof |
| CN117728034B (en) * | 2024-02-07 | 2024-05-24 | 新乡华锐锂电新能源股份有限公司 | Lithium ion battery electrolyte capable of being subjected to rate discharge at ultralow temperature and preparation method thereof |
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Denomination of invention: A 5V high voltage electrolyte for lithium ion battery with nickel lithium manganate cathode Effective date of registration: 20220526 Granted publication date: 20200911 Pledgee: Henan shuoen Electric Appliance Co.,Ltd. Pledgor: HENAN HUARUI ADVANCED MATERIALS CO.,LTD. Registration number: Y2022980006404 |