CN111978183B - Difluorophosphate, preparation method thereof and application thereof in nonaqueous electrolyte - Google Patents

Difluorophosphate, preparation method thereof and application thereof in nonaqueous electrolyte Download PDF

Info

Publication number
CN111978183B
CN111978183B CN202010827600.0A CN202010827600A CN111978183B CN 111978183 B CN111978183 B CN 111978183B CN 202010827600 A CN202010827600 A CN 202010827600A CN 111978183 B CN111978183 B CN 111978183B
Authority
CN
China
Prior art keywords
difluorophosphate
salt
hexafluorophosphate
preparation
quaternary ammonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010827600.0A
Other languages
Chinese (zh)
Other versions
CN111978183A (en
Inventor
蕫金祥
韩鸿波
吴迎
成青
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huizhou Dado New Material Technology Co ltd
Changde Dadu New Material Co ltd
Original Assignee
Huizhou Dado New Material Technology Co ltd
Changde Dadu New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huizhou Dado New Material Technology Co ltd, Changde Dadu New Material Co ltd filed Critical Huizhou Dado New Material Technology Co ltd
Priority to CN202010827600.0A priority Critical patent/CN111978183B/en
Publication of CN111978183A publication Critical patent/CN111978183A/en
Application granted granted Critical
Publication of CN111978183B publication Critical patent/CN111978183B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • 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
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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 discloses a difluorophosphate, which has a structural general formula shown in formula (I):
Figure DDA0002636794270000011
in formula (I): r is R 1‑4 ＝CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、CH 2 CH 2 CN、CH 2 CH 2 OCH 3 Allyl, propargyl, aryl. The invention also discloses a preparation method of the difluorophosphate and application of the difluorophosphate in non-aqueous electrolyte, and a battery containing the difluorophosphate electrolyte provided by the invention has obviously improved battery performance.

Description

Difluorophosphate, preparation method thereof and application thereof in nonaqueous electrolyte
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a preparation method of difluorophosphate and application of non-aqueous electrolyte containing the difluorophosphate in an electrochemical energy storage device.
Background
The lithium ion battery electrolyte generally consists of electrolyte salt, solvent and functional additives. The lithium difluorophosphate is used as a novel lithium ion battery electrolyte additive, and the structural components of the interface film are improved by forming a stable passivation film, so that the internal resistance of the battery is reduced, and the service life of the battery is prolonged. However, lithium difluorophosphate has extremely low solubility, which causes great trouble to the production process of the electrolyte.
Disclosure of Invention
In view of the problems of the prior art, the present invention aims to provide a method for preparing difluorophosphate.
Another object of the present invention is to provide the use of difluorophosphate in nonaqueous electrolytic solutions.
In order to solve the technical problems, the structural general formula of the difluorophosphate is shown as the formula (I):
Figure BDA0002636794260000011
in formula (I):
R 1-4 ＝CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、CH 2 CH 2 CN、CH 2 CH 2 OCH 3 allyl, propargyl, aryl.
The invention provides a preparation method of the difluorophosphate of the formula (I), which comprises the following steps:
(1) Adding hexafluorophosphate and water into a reaction bottle, then adding quaternary ammonium salt, and stirring;
(2) Layering to obtain an organic phase, adding water, repeatedly washing, and drying under reduced pressure to obtain hexafluorophosphate quaternary ammonium salt;
(3) Adding hexafluorophosphate quaternary ammonium salt into a reaction bottle, adding an organic solvent, adding disilyl ether, heating and stirring for reaction;
(4) Drying under reduced pressure to remove the low boiling point solvent and the reactant to obtain the product.
Preferably, the hexafluorophosphate salt in the step (1) comprises alkali metal salt, and the quaternary ammonium salt comprises chloride salt, bromide salt, iodide salt and sulfate.
Preferably, the organic solvent in the step (3) comprises acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, diethyl ether, methyl tertiary butyl ether, ethylene glycol dimethyl ether, dioxane, tetrahydrofuran and dioxolane. The disilyl ether comprises hexamethyldisiloxane, hexaethyldisiloxane and hexapropyldisiloxane.
The difluorophosphate provided by the invention is applied to non-aqueous electrolyte, namely, lithium batteries and lithium ion batteries.
In order to achieve the technical scheme, the invention provides a difluorophosphate electrolyte which comprises conductive lithium salt, a nonaqueous organic solvent, an additive and the difluorophosphate.
Preferably, the mass percentage of the difluorophosphate in the electrolyte is 0.1-90%.
Preferably, the conductive lithium salt further comprises LiBF 4 、LiPF 6 、LiAsF 6 、LiClO 4 、LiSO 3 CF 3 、LiB(C 2 O 4 ) 2 、LiBF 2 C 2 O 4 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 F) 2 One or more of the following.
Preferably, the nonaqueous organic solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate.
Preferably, the additive is one or more of ethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, ethylene sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, succinonitrile, adiponitrile and 1, 2-cyanoethoxy ethane.
The invention also provides a lithium secondary battery: comprises a positive plate, a negative plate, a diaphragm and the electrolyte containing difluorophosphate; the positive electrode sheet and the negative electrode sheet contain an active material, a conductive agent, a current collector, and a binder that binds the active material and the conductive agent to the current collector.
Preferably, the positive electrode sheet includesA positive electrode active material capable of reversibly intercalating/deintercalating lithium ions, the positive electrode active material preferably being a lithium composite metal oxide, the metal oxide including oxides of nickel, cobalt, manganese elements, and any ratio combinations thereof; the positive electrode active material further comprises one or more of chemical elements including Mg, al, ti, sn, V, ge, ga, B, zr, cr, fe, sr and rare earth elements; the positive electrode active material further comprises a polyanionic lithium compound LiM x (PO 4 ) y (M is Ni, co, mn, fe, ti, V, x is more than or equal to 0 and less than or equal to 5, y is more than or equal to 0 and less than or equal to 5).
Preferably, the negative electrode sheet includes a negative electrode active material capable of accepting or releasing lithium ions, the negative electrode active material including lithium metal, lithium alloy, crystalline carbon, amorphous carbon, carbon fiber, hard carbon, soft carbon; wherein the crystalline carbon comprises natural graphite, graphitized coke, graphitized MCMB and graphitized mesophase pitch carbon fiber; the lithium alloy comprises an alloy of lithium and aluminum, zinc, silicon, tin, gallium and antimony metals.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with specific embodiments.
The invention is illustrated in more detail below by means of exemplary embodiments. It should be understood that the scope of the invention should not be limited to the scope of the embodiments. Any variations or modifications which do not depart from the gist of the invention will be apparent to those skilled in the art. The scope of the invention is determined by the scope of the appended claims.
Example 1
Figure BDA0002636794260000031
Into a 500mL reaction flask, 92g (0.5 mol) of potassium hexafluorophosphate was added, 400mL of water was added, and the mixture was stirred, 81g (0.5 mol) of dimethyldiallylammonium chloride was added, and the mixture was stirred at room temperature to react for 4 hours. Dichloromethane was added and the lower organic phase was separated, washed three times with deionized water and dried under reduced pressure to give 128.7g of dimethyldiallylhexafluoroammonium phosphate in 95% yield.
A500 mL reaction flask was charged with 67.75g (0.25 mol) of dimethyl diallyl ammonium hexafluorophosphate, 200mL of acetonitrile was added thereto, and the mixture was stirred, 40.5g (0.25 mol) of hexamethyldisiloxane was added thereto, and the mixture was stirred at 60℃for 8 hours. Drying under reduced pressure gave 51.08g of dimethyldiallyldifluoroammonium phosphate in 90% yield.
Example 2
Figure BDA0002636794260000032
Into a 500mL reaction flask, 92g (0.5 mol) of potassium hexafluorophosphate was added, 400mL of water was added, and the mixture was stirred, 81g (0.5 mol) of dimethyl dipropargyl ammonium bromide was added, and the mixture was stirred at room temperature to react for 4 hours. Dichloromethane was added and the lower organic phase was separated, washed three times with deionized water and dried under reduced pressure to give 120.15g of dimethyl dipropargyl ammonium hexafluorophosphate in 90% yield.
Into a 500mL reaction flask, 66.75g (0.25 mol) of dimethyl dipropargyl ammonium hexafluorophosphate was added, 200mL of acetone was added, and the mixture was stirred, 40.5g (0.25 mol) of hexamethyldisiloxane was added, and the mixture was reacted at 70℃for 8 hours. Drying under reduced pressure gave 49.06g of dimethyl dipropargyl ammonium difluorophosphate in 88% yield.
Example 3
Figure BDA0002636794260000041
Into a 500mL reaction flask, 92g (0.5 mol) of potassium hexafluorophosphate was added, 400mL of water was added, and the mixture was stirred, 116g (0.5 mol) of dimethyl dicyanopropyl ammonium bromide was added, and the reaction was stirred at room temperature for 4 hours. Dichloromethane was added and the lower organic phase was separated, washed three times with deionized water and dried under reduced pressure to give 133.65g of dimethyl dicyanopropyl ammonium hexafluorophosphate in 90% yield.
Into a 500mL reaction flask, 74.25g (0.25 mol) of dimethyl dicyanopropyl ammonium hexafluorophosphate was added, 200mL of acetone was added, and the mixture was stirred, 40.5g (0.25 mol) of hexamethyldisiloxane was added, and the mixture was reacted at 70℃for 8 hours. Drying under reduced pressure gave 53.76g of dimethyl dicyanopropyl ammonium difluorophosphate in 85% yield.
Example 4
(1) Preparation of electrolyte
In an argon atmosphere glove box (H 2 O<1 ppm), the mass ratio of the organic solvent to DMC (dimethyl carbonate) is EC (ethylene carbonate): EMC (methylethyl carbonate) =40:40:20 mix, add 12.5% lithium hexafluorophosphate, 1% VC (vinylene carbonate), 2% PS (propane sultone), 3% FEC (fluoroethylene carbonate), 3% SN (succinonitrile) by total weight of electrolyte. The raw materials are added in sequence and fully and uniformly stirred, and the lithium secondary battery electrolyte (free acid) of the invention is obtained<15ppm of water<10ppm)。
(2) Preparation of positive electrode plate
Polyvinylidene fluoride (PVDF) with the mass percentage of 3 percent is dissolved in 1-methyl-2-pyrrolidone solution, liCoO with the mass percentage of 94 percent is added 2 And adding 3% of conductive agent carbon black into the solution, uniformly mixing, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain the positive plate. Other cathode materials LiMn 2 O 4 、LiFePO 4 、LiNi 0.5 Co 0.3 Mn 0.2 、LiNi 0.3 Co 0.3 Mn 0.3 Prepared in the same manner.
(3) Preparation of negative electrode plate
And (3) dissolving the SBR binder with the mass percentage of 4% and the CMC thickener with the mass percentage of 1% in an aqueous solution, adding the graphite with the mass percentage of 95% into the solution, uniformly mixing, coating the mixed slurry on two sides of a copper foil, and drying and rolling to obtain the negative electrode plate. Other negative electrode materials Li 4 Ti 5 O 12 Prepared in a similar manner.
(4) Manufacturing of lithium ion battery
And (3) preparing the prepared positive pole piece, negative pole piece and isolating film into a square battery core in a winding mode, packaging by adopting a polymer, pouring the prepared electrolyte, and preparing the lithium ion battery with the capacity of 1600mAh through processes such as formation and the like.
(5) Battery performance test
Cyclic test conditions: performing charge-discharge cycle test on the battery at a charge-discharge rate of 1/1C; high temperature storage test conditions: firstly, charging and discharging the battery after formation at the normal temperature at 1C, then fully charging the battery at 1C, storing at high temperature, and after the battery is completely cooled, discharging the taken battery at 1C.
Examples 5 to 16 the procedure of example 4 was followed except for the following parameters.
Table 1 examples 4 to 10 and comparative examples 1 to 9
Figure BDA0002636794260000051
Figure BDA0002636794260000061
From the results of examples 4 to 15 and comparative examples 1 to 4, the effect of the additive on the performance of the high-voltage lithium cobaltate and high-nickel ternary battery is relatively large, and from the results of examples 4 to 7, examples 8 to 15 and comparative examples 5 to 9, it is apparent that the improvement of the performance of the battery by the difluorophosphate is relatively remarkable, and the effect of the difluorophosphate quaternary ammonium salt is better than that of the difluorophosphate, probably because the quaternary ammonium salt participates in interfacial film formation. From the results of examples 8 to 15 and comparative examples 8 to 9, it can be seen that the battery performance is remarkably improved by increasing the amount of the difluorophosphate, the solubility of lithium difluorophosphate in the electrolyte is poor, the increased amount brings great trouble to the production of the electrolyte, and the quaternary ammonium difluorophosphate has good solubility.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.

Claims (4)

1. A process for preparing a difluorophosphate comprising the steps of:
(1) Adding hexafluorophosphate and water into a reaction bottle, then adding quaternary ammonium salt, and stirring;
(2) Layering to obtain an organic phase, adding water, repeatedly washing, and drying under reduced pressure to obtain hexafluorophosphate quaternary ammonium salt;
(3) Adding hexafluorophosphate quaternary ammonium salt into a reaction bottle, adding an organic solvent, adding disilyl ether, heating and stirring for reaction;
(4) Drying under reduced pressure to remove low boiling point solvent and reactant to obtain the product;
the structural general formula of the difluorophosphate is shown in the formula (I):
Figure QLYQS_1
（I）
in formula (I):
R 1-4 =CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、CH 2 CH 2 CN、CH 2 CH 2 OCH 3 allyl, propargyl, aryl.
2. A process for the preparation of difluorophosphate as claimed in claim 1 wherein: the hexafluorophosphate in the step (1) is alkali metal salt, and the quaternary ammonium salt is one or more of chloride salt, bromide salt, iodized salt and sulfate.
3. A process for the preparation of difluorophosphate as claimed in claim 1 wherein: the organic solvent in the step (3) is one or more of acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, diethyl ether, methyl tertiary butyl ether, ethylene glycol dimethyl ether, dioxane, tetrahydrofuran and dioxolane.
4. A process for the preparation of difluorophosphate as claimed in claim 1 wherein: the disilyl ether in the step (3) is one or more of hexamethyldisiloxane, hexaethyldisiloxane and hexapropyldisiloxane.
CN202010827600.0A 2020-08-17 2020-08-17 Difluorophosphate, preparation method thereof and application thereof in nonaqueous electrolyte Active CN111978183B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010827600.0A CN111978183B (en) 2020-08-17 2020-08-17 Difluorophosphate, preparation method thereof and application thereof in nonaqueous electrolyte

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010827600.0A CN111978183B (en) 2020-08-17 2020-08-17 Difluorophosphate, preparation method thereof and application thereof in nonaqueous electrolyte

Publications (2)

Publication Number Publication Date
CN111978183A CN111978183A (en) 2020-11-24
CN111978183B true CN111978183B (en) 2023-06-20

Family

ID=73434581

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010827600.0A Active CN111978183B (en) 2020-08-17 2020-08-17 Difluorophosphate, preparation method thereof and application thereof in nonaqueous electrolyte

Country Status (1)

Country Link
CN (1) CN111978183B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104810550A (en) * 2014-06-13 2015-07-29 万向A一二三***有限公司 Preparation method of functional additive-containing lithium ion battery
CN105074994A (en) * 2013-03-27 2015-11-18 三菱化学株式会社 Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same
CN106025175A (en) * 2016-06-15 2016-10-12 中国科学院宁波材料技术与工程研究所 Battery slurry, battery pole piece and preparation method of battery pole piece

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105074994A (en) * 2013-03-27 2015-11-18 三菱化学株式会社 Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same
CN104810550A (en) * 2014-06-13 2015-07-29 万向A一二三***有限公司 Preparation method of functional additive-containing lithium ion battery
CN106025175A (en) * 2016-06-15 2016-10-12 中国科学院宁波材料技术与工程研究所 Battery slurry, battery pole piece and preparation method of battery pole piece
WO2017215121A1 (en) * 2016-06-15 2017-12-21 中国科学院宁波材料技术与工程研究所 Battery paste, battery electrode plate, and preparation method therefor

Also Published As

Publication number Publication date
CN111978183A (en) 2020-11-24

Similar Documents

Publication Publication Date Title
CN108808087B (en) Electrolyte containing lithium phosphoryl imide and battery using electrolyte
US20080118847A1 (en) Rechargeable lithium battery
WO2020063371A1 (en) Positive electrode piece and lithium-ion secondary battery
JP2004139743A (en) Nonaqueous electrolyte secondary battery
CN106785048B (en) A kind of electrolyte containing pyridine ring sulfimide lithium and the battery using the electrolyte
CN111333595A (en) Lithium acetylsulfanilate, preparation method thereof and application thereof in non-aqueous electrolyte
US20140315089A1 (en) Positive active material, method of preparing the same, and rechargeable lithium battery including the same
CN113135947B (en) Lithium acetylsulfanilate complex, preparation method thereof and application thereof in non-aqueous electrolyte
US9337479B2 (en) Nonaqueous electrolyte secondary battery
KR20190118964A (en) Non-aqueous electrolyte solution and lithium secondary battery comprising the same
JP7378601B2 (en) Non-aqueous electrolyte for lithium secondary batteries and lithium secondary batteries containing the same
US9153842B2 (en) Rechargeable lithium battery including positive electrode including activated carbon and electrolyte containing propylene carbonate
CN114989059B (en) Lithium ion battery lithium supplementing agent and preparation method and application thereof
JP6233828B2 (en) Negative electrode for lithium ion battery, lithium ion battery comprising the negative electrode
JP7350416B2 (en) Non-aqueous electrolyte for lithium secondary batteries and lithium secondary batteries containing the same
JP4082853B2 (en) Lithium secondary battery
CN103178265A (en) Positive active material, method of preparing the same, and rechargeable lithium battery
KR101523081B1 (en) Complex of positive electrode active material and fluorine compound, manufacturing method of the same, and rechargable lithium battery including the complex
CN109873201B (en) Non-aqueous electrolyte and lithium ion battery
CN116323628B (en) Compound, electrolyte for secondary battery comprising the compound, and secondary battery comprising the electrolyte
CN108615942A (en) Application containing (fluoro) methylene-disulfonic acid lithium salts and preparation method thereof and in nonaqueous electrolytic solution
CN111978183B (en) Difluorophosphate, preparation method thereof and application thereof in nonaqueous electrolyte
JP7350415B2 (en) Non-aqueous electrolyte for lithium secondary batteries and lithium secondary batteries containing the same
CN115172878A (en) Electrolyte, preparation method thereof and secondary battery
US20210043931A1 (en) Positive active material precursor for rechargeable lithium battery, positive active material for rechargeable lithium battery, method of preparing the positive active material, and rechargeable lithium battery including the positive active material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant