CN106654242A - High-voltage lithium battery with silicon-based negative electrode - Google Patents
High-voltage lithium battery with silicon-based negative electrode Download PDFInfo
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- CN106654242A CN106654242A CN201710049194.8A CN201710049194A CN106654242A CN 106654242 A CN106654242 A CN 106654242A CN 201710049194 A CN201710049194 A CN 201710049194A CN 106654242 A CN106654242 A CN 106654242A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- 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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
Abstract
The invention provides a high-voltage lithium secondary battery. The high-voltage lithium secondary battery comprises a negative electrode, a positive electrode, a separator and a non-aqueous electrolyte, wherein the separator and the non-aqueous electrolyte are arranged between the negative electrode and the positive electrode, an active substance of the negative electrode is a lithium transition metal oxide, an active substance of the positive electrode is a mixture containing elemental silicon or silicon oxide, the separator is a polyethylene (PE), polypropylene (PP) or ceramic separator, the non-aqueous electrolyte comprises a non-aqueous organic solvent, a lithium salt and an additive, and the additive comprises fluoroethylene carbonate (FEC), 1,3,5-triallyl isocyanurate and a dinitrile compound. Compared with the prior art, the high-voltage lithium secondary battery has the advantages that by a synergistic effect generated by combined application of the three additives, the physical and chemical structural stability of an electrode surface is improved, so that the high-voltage lithium battery with a silicon-based negative electrode has relatively good high-temperature storage performance and cycle performance.
Description
Technical field
The present invention relates to lithium ion battery preparing technical field, and in particular to a kind of silicon-based anode high-voltage lithium.
Background technology
Lithium ion battery is the battery of a new generation's most competitiveness, is referred to as " the environmental protection energy ", is to solve contemporary ring
Border pollution problem and the one preferred technique of energy problem.In recent years, in high-energy battery field lithium ion battery achieved with huge
Success, but consumer still expects that the higher battery of combination property emerges, and this is depended on to new electrode material and electrolyte
The research and development of system.
At present the electronic digital product such as smart mobile phone, panel computer requires more and more higher to the energy density of battery so that
Commercial li-ion battery is difficult to meet and requires.The energy density for lifting battery can be by following two modes：
1. high power capacity and high-pressure solid positive and negative pole material are selected；
2. the operating voltage of battery is improved.
Pure silicon-based anode theory gram volume can high 4200mAh/g, but the negative pole as lithium battery, due to bulk effect, electricity
Pond expansion, efflorescence are extremely serious, and cycle performance is poor, and then, people consider to be combined silicon carbon material, form silicon-carbon cathode material
Material, can largely improve the specific capacity of material, while the bulk effect of silica-base material can be to a certain extent reduced,
And the electrolyte matched with silicon-carbon cathode material also arises at the historic moment, become the focus of lithium battery electrolytes research, it is negative with graphite
Pole is compared, and because silicon has a bulk effect, battery occurs volumetric expansion in cyclic process, and pole piece efflorescence is so as to causing battery
Capacity attenuation is rapid, and cycle life is poor, and matching electrolyte needs the bulk effect for suppressing silicon to a certain extent, so as to
Ensure the good stable circulation of silicon-carbon cathode.In addition, it is also desirable to take into account good high-temperature behavior, to meet high energy density cells
Application under the high temperature conditions.
Fluorinated ethylene carbonate (FEC) can form uniform SEI films on silicon-carbon cathode surface, due to silicon-carbon cathode material
Particularity, its initial is destroyed due to bulk effect, it is follow-up need further to be formed repair, it is past in its electrolyte system
It is past to need film for additive more more than graphite cathode system, it usually needs using more FEC additives, but FEC is in height
Easily thermally decomposed in warm environment, it is impossible to meet battery high-temperature use requirement etc., fluorinated ethylene carbonate is used alone
(FEC), there are various disadvantages in it.
Open ether/the virtues containing two itrile groups of United States Patent (USP) US 2008/0311481Al (Samsung SDI Co., Ltd)
Based compound, improves inflatable of the battery under high voltage and hot conditions, improves high-temperature storage performance, its battery performance need into
One step is improved.For example simultaneously when requiring that cycle performance is further improved with high-temperature storage performance, both results occur lance
Shield.
The A of Samsung SDI Co., Ltd CN 105428712 are disclosed to be contained based on Si negative electrode active material lithium rechargeable batteries
There is additive to include TFMS lithium and fluoroethylene carbonate, improve the reciprocal characteristics and cycle life of Si negative batteries
Characteristic.But, this invention needs further to lift the high-temperature behavior of Si negative batteries and meets high energy density cells in height
Application under the conditions of temperature.
In view of this, it is necessory to provide one kind improve silicon-based anode high-voltage lithium under high voltages good stability,
The electrolyte method and its battery of circulation and high-temperature behavior are taken into account simultaneously.
The content of the invention
For not enough present in background above technology, the invention provides a kind of silicon-based anode high-voltage lithium ion is electric
Pond.
To achieve these goals, the present invention is achieved through the following technical solutions：
A kind of silicon-based anode high-voltage lithium, including：Negative electrode, anode, the barrier film being placed between negative electrode and anode and non-
Water electrolysis liquid, it is characterised in that；
The active material of negative electrode is lithium transition-metal oxide；
The active material of anode is the mixture containing elementary silicon or silica；
Barrier film is polyethylene (PE), polypropylene (PP) or ceramic diaphragm；
The nonaqueous electrolytic solution includes：Non-aqueous organic solvent, lithium salts and additive, additive includes fluoro ethylene carbonate
Ester, 1,3,5- Triallyl isocyanurates and dinitrile compound shown at least one Formulas I；
Formulas I：
Wherein, R represents the group that carbon number is 1～10；R is independently selected from alkylene, ethyoxyl, phenyl, vinyl
Group in one kind；
Active material-the lithium transition-metal oxide of negative electrode is Li1+aNixCoyMnzL(1-x-y-z)O2, wherein L be Al, Sr,
One kind in Mg, Ti, Ca, Zr, Zn, Si and Fe, 0≤x≤1,0≤y≤1,0≤z≤1,0≤a≤1.
The active material of the anode is the silicon-carbon that nano-silicon or SiOx are composited with graphite.
The barrier film adopts polyethylene (PE), polypropylene (PP) polymeric membrane or ceramic diaphragm；It is preferred that one side is coated with
Al2O3Ceramic diaphragm, or the ceramic diaphragm of dual coating PVDF.
It is 6%～26% percentage by weight that the content of the fluorinated ethylene carbonate presses the gross weight meter of nonaqueous electrolytic solution.
Described 1, it is 0.01%～2% that the content of 3,5- Triallyl isocyanurates presses the gross weight meter of nonaqueous electrolytic solution
Percentage by weight.
Dinitrile compound shown in the Formulas I, is 0.1%～6% by the gross weight meter of nonaqueous electrolytic solution.
The electrolyte also contains PS, Isosorbide-5-Nitrae-butane sultone, propenyl-1,3-sulfonic acid lactone and sulphur
Vinyl acetate one or more, and above-mentioned each additive mass percent in the electrolytic solution be respectively 0.1%～
10%.
The lithium salts is selected from lithium hexafluoro phosphate, lithium perchlorate, LiBF4, double fluorine Lithium bis (oxalate) borates, double oxalic acid boric acid
One or more in lithium, two (trimethyl fluoride sulfonyl) imine lithiums and imidodisulfuryl fluoride lithium salt.
Lithium salts is the lithium hexafluoro phosphate of concentration 1.15mol/L in the nonaqueous electrolytic solution.
Described non-aqueous organic solvent is selected from ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, carbon
Diethyl phthalate, methyl ethyl carbonate, methyl propyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate,
One kind in propyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, 6-caprolactone or two
More than kind.
It is an advantage of the current invention that：
(1) in additive 6%-26% fluorinated ethylene carbonate (FEC), form stable and with toughness in silicon-based anode
SEI films, bear battery during repeated charge silicon produce volumetric expansion, it is ensured that battery has preferable cyclicity
Energy.
(2) in additive 0.01%-2% 1,3,5- Triallyl isocyanurates, three in the middle of this compound N originals
Son respectively has a pair of lone pair electrons, effectively can be complexed with high-valency metal atom, can significantly reduce the interface impedance of positive pole, favorably
In lithium ion positive pole interface migration, and the complexing of N atoms and high-valency metal atom significantly reduces positive electrode pair
The oxidation activity of electrolyte, so as to improve high-temperature storage performance of lithium ion battery.
(3) in additive 0.1%-6% dinitrile compound, can with metal ion occur complexing, reduce electrolysis
Liquid decomposes, and suppresses digestion of metallic ion, protects positive pole, lifts battery performance.
(4) lithium-ion battery electrolytes of the invention have so that silicon-carbon cathode lithium ion battery still keeps under high voltages
The beneficial effect of good cycle life, cryogenic discharging characteristic and high-temperature storage characteristics.
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 scope of embodiment, any change 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.
Embodiment 1
1st, the preparation method of the present embodiment high-voltage lithium ion batteries, according to done battery size (PL454261), design
Capacity and positive and negative pole material gram volume etc. determine coated face density.Positive active material is purchased from the leading 4.4V cobalt acid lithiums material of Beijing University
Material；Negative electrode active material purchased from Shenzhen Bei Terui productions silicon-based anode (silicone content in silicon based anode material accounts for 1%～
15%).
Its positive pole preparation process, negative pole preparation process, electrolyte preparation process, barrier film preparation process and battery number of assembling steps
It is described as follows：
The positive pole preparation process is：By 96.8: 2.0: 1.2 mass ratio mixing high-voltage anode active material cobalt acid
Lithium, conductive carbon black and binding agent polyvinylidene fluoride, in being dispersed in METHYLPYRROLIDONE, obtain anode sizing agent, by positive pole
Slurry is uniformly coated on the two sides of aluminium foil, through drying, calendering and be vacuum dried, and with supersonic welder burn-on aluminum draw
Positive plate is obtained after line, the thickness of pole plate is between 100-115 μm；
The negative pole preparation process is：By 96: 1: 1.2: 1.8 quality than admixed graphite, conductive carbon black, binding agent butylbenzene
Rubber and carboxymethylcellulose calcium, dispersion in deionized water, obtains cathode size, and cathode size is coated on into the two sides of Copper Foil
On, through drying, calendering and it is vacuum dried, and burn-on with supersonic welder and obtain negative plate, the thickness of pole plate after nickel lead-out wire
Degree is between 115-135 μm；
The electrolyte preparation process is：By ethylene carbonate, propene carbonate, diethyl carbonate is EC in mass ratio:
Mixed at PC: DEC=10: 20: 70, and the lithium hexafluoro phosphate that concentration is 1.15mol/L is added after mixing, is added and is based on electrolyte
The 1 of gross weight 1wt%, 3,5- Triallyl isocyanurates, the fluorinated ethylene carbonate (FEC) of 15wt%, 3wt% oneself two
Nitrile, 0.5%1,2- bis- (2- cyanoethoxyls) ethane.
The barrier film preparation process is：Barrier film is coated with Al using one side2O3, ceramic diaphragm；
The preparation of lithium ion battery：Obtained positive plate, barrier film, negative plate are folded in order, barrier film is made in positive and negative
In the middle of pole piece, winding obtains naked battery core；Naked battery core is placed in external packing, the electrolyte of above-mentioned preparation is injected into dried
In battery, encapsulation, standing, chemical conversion, shaping, partial volume complete the preparation (model 454261PL) of lithium ion battery.
1) normal-temperature circulating performance test：At 25 DEG C, the cobalt acid lithium battery after chemical conversion is charged into 4.4V with 1C constant current constant voltages,
Then with 1C constant-current discharges to 3.0V.The conservation rate of the 500th circulation volume, computing formula are calculated after 500 circulations of charge/discharge
It is as follows：
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/1st time cyclic discharge capacity) ×
100%；
2) high-temperature storage performance：Battery after chemical conversion is charged into 4.4V with 0.5C constant current constant voltages at normal temperatures, battery is measured
Then original depth, initial discharge capacity stores 4h at 85 DEG C, and battery final thickness is tested under the conditions of 85 DEG C, calculates battery thick
Degree expansion rate；The holding capacity and recovery capacity of 3.0V measurement batteries are discharged to after cooling with 0.5C.Computing formula is as follows：
Cell thickness expansion rate (%)=(final thickness-original depth)/original depth × 100%；
Battery capacity conservation rate (%)=holding capacity/initial capacity × 100%；
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%.
3) low temperature discharge：With 1C constant-current constant-voltage chargings to 4.4V (cut-off current is as 0.01C) under 25 DEG C of environment, shelve
5min, 0.2C are discharged to 3.0V, detect battery initial capacity.Shelve 5min, (cut-off current is 1C constant-current constant-voltage chargings to 4.4V
0.01C).Battery is put into -20 DEG C of high-low temperature chamber and shelves 6h, and with this understanding 3.0V is discharged to 0.2C, detected low
Discharge capacity under temperature.
Low temperature discharge conservation rate (%)=low temperature discharge capacity/initial capacity × 100%；
2nd, embodiment 2～15
Embodiment 2～15, in addition to additive composition presses addition shown in table 1 with content (being based on electrolyte gross weight), its
It is same as Example 1.In table 1,3-PS be PS, PRS be propenyl-1,3-sulfonic acid lactone, AN be oneself
Dintrile, SN are succinonitrile, DTD is sulfuric acid vinyl ester, DCB is 3- hexene dintrile, BCN is 1,2- bis- (2- cyanoethoxyls) ethane,
PEN is 1,3- benzene diacetonitriles.
There is more preferable normal-temperature circulating performance, high-temperature storage using the 1～embodiment of embodiment 15 of technical scheme
And low temperature performance.High/low temperature and cycle performance can not simultaneously be taken into account using the battery of the electrolyte of 1～comparative example of comparative example 6,
Combination property is poor.
Embodiment 1 is with comparative example 1, comparative example 2 and comparative example 3；Embodiment 14 is with comparative example 4, comparative example 5 and comparative example 6
Relatively understand：
Comparative example 1 without FEC and the circle normal temperature circulation conservation rate of comparative example the 4, the 500th are respectively 21.8% and 38.6%,
Far below embodiment 1 (80.6%) and embodiment 14 (86.6%), corresponding high-temperature storage and low temperature performance are poor.Due to
FEC can form SEI films stable and with toughness in silicon-based anode, bear the battery body that silicon is produced during repeated charge
Product expansion, it is ensured that battery has preferable cycle performance, while improving low temperature performance.Illustrate fluorinated ethylene carbonate
(FEC) presence, can integrally lift the output performance of battery.
Without 1, after the comparative example 2 of 3,5- Triallyl isocyanurates and the storage 4 hours of 5,85 DEG C of comparative example, battery gas
Swollen obvious, hot Thickness Measurement by Microwave expansion rate is higher than 20%；Low temperature performance is slightly better than embodiment, normal-temperature circulating performance and embodiment phase
When.The presence of 1,3,5- Triallyl isocyanurates is illustrated, the gas production during high-temperature storage can be substantially reduced, lifted
The high-temperature storage performance of lithium ion battery；But its viscosity is higher, add in electrolyte has negative effect to cryogenic property.
Comparative example 3 without dinitrile compound and comparative example 6, under the conditions of high voltage (4.4V), positive pole can not be had
Effect protection, causes digestion of metallic ion, and electrolyte is serious with positive pole side reaction, causes battery performance (normal-temperature circulating performance and height
Warm storge quality) deterioration.The presence of dinitrile compound is illustrated, complexing can be occurred with metal ion and then be protected positive pole,
Electrolyte decomposition is reduced, suppresses digestion of metallic ion, lift battery performance.
It is further advanced by each embodiment to find with the contrast of comparative example 1-6, by being used in combination for three of the above additive
Produced cooperative effect, so as to substantially increase silicon-based anode lithium ion battery output characteristics, it is ensured that battery is under high voltages
Still keep good cycle life, cryogenic discharging characteristic and high-temperature storage characteristics.
It is more than to illustrate for the possible embodiments of the present invention, but the embodiment and is not used to limit the present invention's
The scope of the claims, all equivalence enforcements or change without departing from carried out by the technology of the present invention spirit, is intended to be limited solely by the patent model of the present invention
Within enclosing.
Claims (9)
1. a kind of silicon-based anode high-voltage lithium, including：Negative electrode, anode, the barrier film being placed between negative electrode and anode and non-aqueous
Electrolyte, it is characterised in that：
The active material of negative electrode is lithium transition-metal oxide；
The active material of anode is the mixture containing elementary silicon or silica；
Barrier film is polyethylene (PE), polypropylene (PP) or ceramic diaphragm；
The nonaqueous electrolytic solution includes：Non-aqueous organic solvent, lithium salts and additive, additive include fluorinated ethylene carbonate, 1,
3,5- Triallyl isocyanurates and dinitrile compound shown at least one Formulas I
Formulas I：
Wherein, R represents the group that carbon number is 1～10；R independently selected from alkylene, ethyoxyl, phenyl, vinyl base
One kind in group.
2. silicon-based anode high-voltage lithium according to claim 1, it is characterised in that：The active material lithium transition of negative electrode
Metal oxide is Li1+aNixCoyMnzL(1-x-y-z)O2, wherein L be Al, the one kind in Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe,
0≤x≤1,0≤y≤1,0≤z≤1,0≤a≤1.
3. silicon-based anode high-voltage lithium according to claim 1, it is characterised in that：The active material of the anode is
The silicon-carbon that nano-silicon or SiOx are composited with graphite.
4. silicon-based anode high-voltage lithium according to claim 1, it is characterised in that：The barrier film is coated using one side
There is Al2O3Ceramic diaphragm or dual coating PVDF ceramic diaphragm.
5. silicon-based anode high-voltage lithium according to claim 1, it is characterised in that：Described 1,3,5- triallyls are different
It is 0.01%～2% that the content of cyanurate presses the gross weight meter of nonaqueous electrolytic solution；The content of the fluorinated ethylene carbonate is pressed
The gross weight meter of nonaqueous electrolytic solution is 6%～26%.
6. silicon-based anode high-voltage lithium according to claim 1, it is characterised in that：Dintrile chemical combination shown in the Formulas I
Thing, is 0.1%～6% by the gross weight meter of nonaqueous electrolytic solution.
7. silicon-based anode high-voltage lithium according to claim 1, it is characterised in that the electrolyte also contains 1,3-
Propane sultone, Isosorbide-5-Nitrae-butane sultone, propenyl-1,3-sulfonic acid lactone and sulfuric acid vinyl ester one or more, and
Above-mentioned each additive mass percent in the electrolytic solution is respectively 0.1%～10%.
8. silicon-based anode high-voltage lithium according to claim 1, it is characterised in that：The lithium salts is selected from hexafluorophosphoric acid
Lithium, lithium perchlorate, LiBF4, double fluorine Lithium bis (oxalate) borates, di-oxalate lithium borate, two (trimethyl fluoride sulfonyl) imine lithiums and double
One or more in fluorine sulfimide lithium salts.
9. silicon-based anode high-voltage lithium according to claim 1, it is characterised in that：Described non-aqueous organic solvent choosing
From ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first third
Ester, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate,
One or more in gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, 6-caprolactone.
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| CN108539270A (en) * | 2018-04-18 | 2018-09-14 | 广州天赐高新材料股份有限公司 | Lithium secondary cell electrolyte and its lithium secondary battery |
| WO2020122158A1 (en) * | 2018-12-12 | 2020-06-18 | 三菱ケミカル株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte cell |
| CN112467219A (en) * | 2020-12-03 | 2021-03-09 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery comprising same |
| CN112467221A (en) * | 2020-12-02 | 2021-03-09 | 珠海市赛纬电子材料股份有限公司 | Additive for inhibiting silicon negative electrode expansion and electrolyte containing additive |
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| CN112467221B (en) * | 2020-12-02 | 2022-02-11 | 珠海市赛纬电子材料股份有限公司 | Additive for inhibiting silicon negative electrode expansion and electrolyte containing additive |
| CN112467219A (en) * | 2020-12-03 | 2021-03-09 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery comprising same |
| CN112467219B (en) * | 2020-12-03 | 2022-03-29 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery comprising same |
| CN114628773A (en) * | 2020-12-14 | 2022-06-14 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| CN112993379A (en) * | 2021-02-04 | 2021-06-18 | 重庆市紫建新能源有限公司 | High-energy-density quick-charging polymer lithium ion battery and preparation method thereof |
| CN114597492A (en) * | 2021-04-12 | 2022-06-07 | 深圳市研一新材料有限责任公司 | Nonaqueous electrolyte solution and lithium ion battery using same |
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