CN109970981A - A kind of solid fireproof polymer, electrode slice, diaphragm and lithium secondary battery - Google Patents
A kind of solid fireproof polymer, electrode slice, diaphragm and lithium secondary battery Download PDFInfo
- Publication number
- CN109970981A CN109970981A CN201711444931.0A CN201711444931A CN109970981A CN 109970981 A CN109970981 A CN 109970981A CN 201711444931 A CN201711444931 A CN 201711444931A CN 109970981 A CN109970981 A CN 109970981A
- Authority
- CN
- China
- Prior art keywords
- halogenated
- sub
- group
- lithium secondary
- secondary battery
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
-
- 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
- H01M10/42—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The embodiment of the invention provides a kind of solid fireproof polymer, including the repetitive unit containing three phosphonitrile structure of ring, are polymerized by the monomer containing three phosphonitrile structure of ring by chemical bond grafting, shown in general formula such as formula (I) or formula (II),X is selected from alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, alkenylene, haloalkenediyl, sub- alkenyloxy group, halogenated sub- alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group, replaces phosphoric acid Asia ester group, substituted imides base or replace sulfimide base；Y is selected from oxygen, sulphur, alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, alkenylene, haloalkenediyl, sub- alkenyloxy group, halogenated sub- alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group, replaces phosphoric acid Asia ester group, substituted imides base or replace sulfimide base.The present invention also provides lithium secondary battery electrode piece, diaphragm and lithium secondary batteries.
Description
Technical field
The present invention relates to lithium secondary battery technical fields, more particularly to a kind of solid fireproof polymer, electrode slice, diaphragm
And lithium secondary battery.
Background technique
Lithium secondary battery is due to energy density height, operating voltage height, long service life, self-discharge rate are low and environmental-friendly etc.
Advantage is widely used in portable electronic product (smart phone, digital camera, laptop etc.), with
The fast development of the New Energy Industries such as electric car and extensive energy storage power grid, higher want is proposed to battery energy density
It asks, wherein exploitation height ratio capacity positive and negative pole material and high-voltage anode material are the current masters for promoting lithium secondary battery energy density
Want technological means.However the use of height ratio capacity and high voltage material is focused on, the peace of liquid lithium secondary battery will certainly be brought
Full problem.The electrolyte of lithium secondary battery is mainly non-aqueous organic electrolyte (conventional is carbonates electrolyte), when battery exists
Because there are the hidden danger such as volatile, easy firing, poles for its electrolyte under abuse (thermal shock overcharges, needle thorn and external short circuit etc.) state
Easily cause safety issue caused by battery thermal runaway.
Currently, improving the method that liquid safety of lithium secondary battery generally uses is the directly addition resistance into conventional electrolysis liquid
The conductivity and increasing of electrolyte can be reduced although the flame resistance of electrolyte can be improved in the addition of fire retardant by firing additive
Add the viscosity of electrolyte, while side reaction can occur during circulating battery for the fire retardant, thus to the electrochemistry of battery
Certain negative effect can be caused.Therefore, direct in order to solve safety issue existing for liquid lithium secondary battery and fire retardant
It is added to brought negative effect in electrolyte, really it is necessary to develop a kind of new flame retardant, had both been avoided that in electrolyte
In use again can improve the safety of lithium secondary battery, while have with the good compatibility of positive and negative pole material, do not influence lithium
The cycle performance of secondary cell.
Summary of the invention
In consideration of it, first aspect of the embodiment of the present invention provides a kind of solid fireproof polymer, with excellent fire-retardant
Performance, do not dissolve in lithium secondary cell electrolyte, have with the good compatibility of positive and negative pole material, can be directly incorporated into positive and negative anodes or every
In film, cycle performance of battery is not influenced while improving battery security, to solve in the prior art directly by flame-retardant additive
Being added in electrolyte, which leads to be electrolysed fluid viscosity, increases, and impedance increases, final the problem of influencing lithium secondary battery chemical property.
Specifically, first aspect of the embodiment of the present invention provides a kind of solid fireproof polymer, the solid fireproof polymerization
Object includes the repetitive unit containing three phosphonitrile structure of ring, is graft-polymerized by the monomer containing three phosphonitrile structure of ring by chemical bond
At, shown in the general formula such as formula (I) or formula (II) of the solid fireproof polymer,
In formula (I), the X is selected from alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, alkenylene, halogenated
Alkenylene, halogenated sub- alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group, replaces phosphoric acid at sub- alkenyloxy group
Sub- ester group, substituted imides base, replace sulfimide base in any one；The R1、R2、R3、R4Be respectively selected from fluorine, chlorine,
It is bromine, alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy group, haloalkenyloxy, aryl, halogenated
Aryl, aryloxy group, any one in haloaryloxy；
In formula (II), the Y is selected from oxygen, sulphur, alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, sub- alkene
Base, haloalkenediyl, sub- alkenyloxy group, halogenated sub- alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group,
Replace phosphoric acid Asia ester group, substituted imides base, replace sulfimide base in any one；The R1’、R2’、R3’、R4’、R5’
It is respectively selected from fluorine, chlorine, bromine, alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy group, haloalkene
Oxygroup, aryl, halogenated aryl, aryloxy group, any one in haloaryloxy.
In first aspect present invention, in the X and the Y, the alkylidene, halogeno alkylen, alkylene oxide group, halogenated Asia
The carbon atom number of alkoxy is 1-20；The alkenylene, haloalkenediyl, sub- alkenyloxy group, the carbon atom number of halogenated sub- alkenyloxy group
For 2-20；The arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group carbon atom number be 6-20；The substitution phosphorus
The carbon atom number of sour Asia ester group, substituted imides base and the substituent group in substitution sulfimide base is 1-20.
In first aspect present invention, in the X and the Y, the halogeno alkylen, halo alkyleneoxy, halogenated sub- alkene
Base, halogenated sub- alkenyloxy group, halogenated arlydene, the halogen in halogenated sub- aryloxy group include fluorine, chlorine, bromine, iodine, it is described it is halogenated be perhalogeno
Generation or partially halogenated.
In first aspect present invention, the R1、R2、R3、R4、R1’、R2’、R3’、R4' and R5' in, the alkyl, alkyl halide
Base, alkoxy, halogenated alkoxy carbon atom number be 1-20；The alkenyl, halogenated alkenyl, alkenyloxy group, haloalkenyloxy carbon
Atomicity is 2-20；The aryl, halogenated aryl, aryloxy group, haloaryloxy carbon atom number be 6-20.
In first aspect present invention, the R1、R2、R3、R4、R1’、R2’、R3’、R4' and R5' in, the halogenated alkyl, halogen
It include fluorine, chlorine, bromine, iodine for the halogen in alkoxy, halogenated alkenyl, haloalkenyloxy, halogenated aryl, haloaryloxy, it is described
Halogenated is perhalogeno or partially halogenated.
In first aspect present invention, in the formula (I), n 2-1000.
In first aspect present invention, in the formula (II), n 2-1000.
In first aspect present invention, the X and the Y are respectively selected from-CH2(methylene) ,-CH2CH2(ethylidene) ,-
CH2CH2CH2(propylidene) ,-C (CH3)2(isopropylidene) ,-CH2CH2CH2CH2(butylidene) ,-CH2CH2CH=CH- (sub- 1-
Cyclobutenyl) ,-CF2CF2CF2CF2(perfluor replaces Aden's alkyl) ,-OCH2CF2(difluoro substitution inferior ethoxyl), methyl Asia benzene
Base, vinyl phenylene, fluoro substituted phenylen or-OP=O (OCH3) O- (methyl acid phosphate Asia ester group) ,-OP=O (OCH2CF3)O-
(trifluoroethyl phosphoric acid Asia ester group) ,-NHC (=O) CH2(sub- acetylimino) and-NHS (=O)2CF2(difluoro methylene sulphur
Imide) in any one.
The solid fireproof polymer that first aspect of the embodiment of the present invention provides, is passed through by the monomer containing three phosphonitrile structure of ring
Chemical bond grafting is polymerized, and has excellent flame retardant property, and do not dissolve in lithium secondary cell electrolyte, has and positive and negative anodes material
Expect good compatibility, can be directly incorporated into anode and cathode slurry and positive and negative anodes pole piece is made, or diaphragm table is integrated to by binder
Face is finally applied to lithium secondary battery, improves battery security, and guarantee that cycle performance of battery is unaffected.
Second aspect of the embodiment of the present invention provides a kind of lithium secondary battery electrode piece, including collector and setting exist
Electrode active material layers on the collector include solid described in first aspect present invention in the electrode active material layers
Flame-retardant polymer.
In second aspect of the present invention, the solid fireproof polymer accounts for the 0.1%- of the electrode active material layers gross mass
20%.
In second aspect of the present invention, the solid fireproof polymer is dispersed in the electrode active material layers.
In second aspect of the present invention, the lithium secondary battery electrode piece includes cathode plate for lithium secondary battery pole piece or the secondary electricity of lithium
Pond cathode pole piece.
The third aspect of the embodiment of the present invention provides a kind of diaphragm, the diaphragm include septum body and be set to it is described every
The flame-retardant layer on membrane body one or both sides surface, the material of the flame-retardant layer include solid fireproof described in first aspect present invention
Polymer and binder.
In third aspect present invention, in the flame-retardant layer, the mass ratio of the solid fireproof polymer and the binder
For 1-100:1.
In third aspect present invention, the flame-retardant layer with a thickness of 0.1 μm -10 μm.
In third aspect present invention, the binder includes Kynoar (PVDF), polymethyl methacrylate
(PMMA), polytetrafluoroethylene (PTFE) (PTFE), Kynoar-hexafluoropropene (PVDF-HFP), polyacrylonitrile (PAN), polyimides
(PI), polyethylene glycol (PEG), Pluronic F-127 (PEO), poly-dopamine (PDA), sodium carboxymethylcellulose/butadiene-styrene rubber (CMC/
SBR), polyvinyl alcohol (PVA), polyacrylic acid (PAA), Lithium polyacrylate (LiPAA), polyvinylpyrrolidone (PVP), polylactic acid
(PLA), one of sodium alginate (SA), poly- p styrene sulfonic acid (PSS), poly- p styrene sulfonic acid lithium (LiPSS) and gelatin
Or it is a variety of.
Fourth aspect of the embodiment of the present invention provides a kind of lithium secondary battery, including lithium two described in second aspect of the present invention
Diaphragm described in primary cell electrode slice and/or third aspect present invention.
Detailed description of the invention
Technical solution in order to illustrate the embodiments of the present invention more clearly or in background technique below will be implemented the present invention
Attached drawing needed in example or background technique is illustrated.
Fig. 1 is the preceding 100 weeks cyclic curves for the lithium secondary battery that the embodiment of the present invention 1 is prepared；
Fig. 2 is the preceding 100 weeks cyclic curves for the lithium secondary battery that the embodiment of the present invention 9 is prepared；
Fig. 3 is the preceding 100 weeks cyclic curves for the lithium secondary battery that comparative example 1 is prepared；
Fig. 4 is the preceding 100 weeks cyclic curves for the lithium secondary battery that comparative example 2 is prepared.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, is illustrated to the embodiment of the present invention.
With continually developing for height ratio capacity and high voltage material, the safety problem of liquid lithium secondary battery is increasingly prominent
Out.The core component of lithium secondary battery is mainly anode, cathode, electrolyte and diaphragm, wherein electrolyte is lithium ion positive and negative
The medium transmitted between pole plays an important role the chemical property and security performance of battery.Electrolyte is mainly by conduction
Lithium salts, non-aqueous organic solvent (conventional is carbonate-based solvent) and additive composition.Commercial electrolyte liquid is mainly carbonic ester at present
Class electrolyte, when battery under abuse (thermal shock, overcharge with external short circuit etc.) state because there are volatile, inflammable for its electrolyte
The hidden danger such as burning, easily cause safety issue caused by battery thermal runaway.Currently, most of technologies are mainly to conventional electrolysis
Flame-retardant additive is added in liquid directly to improve the flame resistance of electrolyte, but since the addition of flame-retardant additive can reduce electrolyte
Conductivity and increase electrolyte viscosity, it will certain negative effect is caused to the chemical property of battery.Therefore, it develops
A kind of novel flame-retardant additive gesture that safety of lithium secondary battery can be improved while not influencing lithium secondary battery chemical property exists
It must go.It is not dissolved in consideration of it, the embodiment of the invention provides a kind of solid fireproof polymer with excellent flame retardant property
Lithium secondary cell electrolyte, have with the good compatibility of positive and negative pole material, can be directly incorporated into positive and negative anodes or diaphragm, improve electricity
Cycle performance of battery is not influenced while the safety of pond.
Specifically, the embodiment of the invention provides a kind of solid fireproof polymer, are used for lithium secondary battery, the solid resistance
Firing polymer includes the repetitive unit containing three phosphonitrile structure of ring, is grafted by the monomer containing three phosphonitrile structure of ring by chemical bond
It is polymerized, shown in the general formula such as formula (I) or formula (II) of the solid fireproof polymer,
In formula (I), the X is selected from alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, alkenylene, halogenated
Alkenylene, halogenated sub- alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group, replaces phosphoric acid at sub- alkenyloxy group
Sub- ester group, substituted imides base, replace sulfimide base in any one；The R1、R2、R3、R4Be respectively selected from fluorine, chlorine,
It is bromine, alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy group, haloalkenyloxy, aryl, halogenated
Aryl, aryloxy group, any one in haloaryloxy；
In formula (II), the Y is selected from oxygen, sulphur, alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, sub- alkene
Base, haloalkenediyl, sub- alkenyloxy group, halogenated sub- alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group,
Replace phosphoric acid Asia ester group, substituted imides base, replace sulfimide base in any one；The R1’、R2’、R3’、R4’、R5’
It is respectively selected from fluorine, chlorine, bromine, alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy group, haloalkene
Oxygroup, aryl, halogenated aryl, aryloxy group, any one in haloaryloxy.
Solid fireproof polymer provided in an embodiment of the present invention, with excellent flame retardant property, and it is secondary insoluble in lithium
Battery electrolyte, have with the good compatibility of positive and negative pole material, can be directly incorporated into positive and negative anodes or diaphragm, improve cell safety
Cycle performance of battery is not influenced while property.Specifically, due to containing the elements such as P, N in three phosphonitrile structure of ring, in battery thermal runaway
In the case of, it can decompose and generate H the or OH free radical that P system free radical capture electrolyte is generated by thermal decomposition, cut off chain reaction；Separately
Outside, the NH of generation is decomposed3The free radical and oxygen that equal gaseous matters meeting dilute electrolyte is generated by thermal decomposition, reduce combustible substance
Concentration, so as to inhibit electrolyte burning and improve battery safety, three phosphonitrile structure of ring also with positive and negative pole material
With good compatibility；The flame-retardant polymer is solid polymer, does not dissolve in lithium secondary cell electrolyte, can be with positive and negative anodes
Material stirs slurry and is prepared by mixing into positive and negative anodes pole piece, or avoids in membrane surface by adhesive coated and directly add fire retardant
The negative effect caused by lithium secondary battery performance is added in electrolyte；Therefore, the lithium formed using the solid fireproof polymer
The safety of battery not only can be improved in secondary cell, but also can reduce the negative factor for influencing battery performance.
In embodiment of the present invention, the polymer for leading to formula (I) is to pass through chemical bonding using three phosphonitrile structure of ring as parent
Branch is polymerized；The polymer of logical formula (II) is to be polymerized using three phosphonitrile structure of ring as branch by chemical bond grafting.This
Its stability of the solid fireproof polymer of inventive embodiments and anti-flammability are better than other small molecule phosphonitrile fire retardants, can significantly mention
The security performance of high lithium secondary battery.
In embodiment of the present invention, lead in formula (I) and logical formula (II), in the X and the Y, the alkylidene, halogenated Asia
Alkyl, alkylene oxide group, halo alkyleneoxy carbon atom number are 1-20, further, carbon atom number 1-8；The alkenylene, halogen
Carbon atom number for alkenylene, sub- alkenyloxy group, halogenated sub- alkenyloxy group is 2-20, further, carbon atom number 2-8；The Asia
Aryl, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group carbon atom number be 6-20, further, carbon atom number 6-
10；It is described to replace phosphoric acid Asia ester group, substituted imides base and the carbon atom number of the substituent group in sulfimide base is replaced to be 1-
20, further, carbon atom number is 1-8 or 6-14.
In embodiment of the present invention, in the X and the Y, the halogeno alkylen, halo alkyleneoxy, halogenated sub- alkene
Base, halogenated sub- alkenyloxy group, halogenated arlydene, the halogen in halogenated sub- aryloxy group include fluorine, chlorine, bromine, iodine, it is described it is halogenated be perhalogeno
Generation or partially halogenated.
In embodiment of the present invention, the substituted imides base is represented by-NH-C (=O)-Z1, wherein substituent group Z1
Carbon atom number be 1-20, further, carbon atom number is 1-8 or 6-14, specifically Z1It can be selected from alkylidene, halogenated alkylene
It is base, alkylene oxide group, halo alkyleneoxy, alkenylene, haloalkenediyl, sub- alkenyloxy group, halogenated sub- alkenyloxy group, arlydene, halogenated
Arlydene, sub- aryloxy group, any one in halogenated sub- aryloxy group；The substitution sulfimide base be represented by-NH-S (=
O)2-Z2, wherein substituent group Z2Carbon atom number be 1-20, further, carbon atom number is 1-8 or 6-14, specifically Z2It can
Selected from alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, alkenylene, haloalkenediyl, sub- alkenyloxy group, halogenated Asia
Alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, any one in halogenated sub- aryloxy group.The substituted imides base and
Replace the substituent group containing halogen in sulfimide base, halogen can be fluorine, chlorine, bromine, iodine, it is described it is halogenated can be it is complete
It is halogenated, it is also possible to partially halogenated.It is the alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, alkenylene, halogenated
Alkenylene, sub- alkenyloxy group, halogenated sub- alkenyloxy group can be the branch that is also possible to of straight chain.
In specific embodiment of the present invention, the X and the Y are respectively selected from-CH2(methylene) ,-CH2CH2(sub- second
Base) ,-CH2CH2CH2(propylidene) ,-C (CH3)2(isopropylidene) ,-CH2CH2CH2CH2(butylidene) ,-CH2CH2CH=CH-
(sub- 1- cyclobutenyl) ,-CF2CF2CF2CF2(perfluor replaces Aden's alkyl) ,-OCH2CF2(difluoro substitution inferior ethoxyl), methyl
Phenylene, vinyl phenylene, fluoro substituted phenylen or-OP=O (OCH3) O- (methyl acid phosphate Asia ester group) ,-OP=O
(OCH2CF3) O- (trifluoroethyl phosphoric acid Asia ester group) ,-NHC (=O) CH2(sub- acetylimino) and-NHS (=O)2CF2(two
Fluorine methylene sulfimide base) in any one.
In embodiment of the present invention, the R1、R2、R3、R4、R1’、R2’、R3’、R4' and R5' in, the alkyl, alkyl halide
Base, alkoxy, halogenated alkoxy carbon atom number be 1-20, further, carbon atom number 1-8；The alkenyl, haloalkene
Base, alkenyloxy group, the carbon atom number of haloalkenyloxy are 2-20, further, carbon atom number 2-8；The aryl, halogenated virtue
Base, aryloxy group, haloaryloxy carbon atom number be 6-20, further, carbon atom number 6-10.
In embodiment of the present invention, the R1、R2、R3、R4、R1’、R2’、R3’、R4' and R5' in, halogen or halogen-containing base
Group is conducive to enhance the flame retardant property of electrolysis additive.Wherein, the halogenated alkyl, halogenated alkoxy, halogenated alkenyl, halogenated
Alkenyloxy group, halogenated aryl, the halogen in haloaryloxy include fluorine, chlorine, bromine, iodine, it is described it is halogenated be perhalogeno or partially halogenated.
In the specific embodiment of the invention, the R1、R2、R3、R4、R1’、R2’、R3’、R4' and R5' it can be selected from-OCH3(first
Oxygroup) ,-OCH2CH3(ethyoxyl) ,-OCH2CH2CH3(propoxyl group) ,-OCH (CH3)2(isopropoxy) ,-OCH2CH2CH2CH3(fourth
Oxygroup) ,-OCH2CH2CH=CH2(1- butenyloxy) ,-OCF2CF2CF2CF3(perfluor substitution butoxy) ,-OCH2CF3(trifluoro takes
For ethyoxyl), methylphenoxy, vinyl benzene oxygroup, any one in fluorinated phenoxy.
In embodiment of the present invention, in the formula (I), the R1、R2、R3And R4It can be identical or different group.The formula
(II) in, the R1’、R2’、R3’、R4' and R5' it can also be identical or different group.
In embodiment of the present invention, the degree of polymerization of solid fireproof polymer can be set according to actual needs, and suitable is poly-
It is right to guarantee that polymer has higher stability, it is not readily dissolved in electrolyte and easily preparation.In the formula (I), n can be 2-
1000, it may further be 5-1000,20-200 or 10-100.The solid fireproof polymer molecular weight range can be 1000-
1000000, it further can be 5000-50000 or 2000-30000.
In embodiment of the present invention, in the formula (II), it may further be 5-1000,20-300 that n, which can be 2-1000,.
The solid fireproof polymer molecular weight range can be 1000-1000000, further can be 5000-100000.
In embodiment of the present invention, the solid fireproof polymer can be chain or cyclic polymer.
Further, in specific embodiment of the present invention, the molecular structural formula of the solid fireproof polymer can be such as
Shown in formula (A)-(C):
Solid fireproof polymer provided in an embodiment of the present invention, with excellent flame retardant property, and it is secondary insoluble in lithium
Battery electrolyte, have with the good compatibility of positive and negative pole material, it is stirred into slurry with positive and negative pole material and is prepared by mixing into positive and negative anodes
Pole piece, or by adhesive coated in membrane surface, the safety of battery not only can be improved, but also can be to avoid directly by resistance
Combustion agent is added in electrolyte the negative effect caused by lithium secondary battery performance.
Following synthesis step system can be used in the solid fireproof polymer as shown in formula (I) of the above-mentioned offer of the embodiment of the present invention
It is standby to obtain:
It is separately added into cyclotrinitrile phosphide and solvent into three-necked flask, under the conditions of -20 DEG C -20 DEG C, is burnt to three mouthfuls
It is slowly added to glycol (phenol) sodium compound in bottle, then is stirred to react at 25 DEG C -60 DEG C 6-48 hours, is filtered, is dried under reduced pressure, obtains
The solid fireproof polymer indicated to above-mentioned logical formula (I).
Wherein, the cyclotrinitrile phosphide is depending on the molecular structure of specific solid fireproof polymer to be prepared,
Including but not limited to hexachlorocyclotriph,sphazene, three phosphonitrile of hexafluoro ring, three phosphonitrile of ethyoxyl (five fluorine) ring, three phosphorus of phenoxy group (five fluorine) ring
Nitrile etc..The solvent includes but is not limited to ethane, hexamethylene, methylene chloride, chloroform, ether, petroleum ether, benzene, toluene, chlorine
Benzene, fluorobenzene, acetone, acetonitrile, methanol, ethyl alcohol, tetrahydrofuran, nitromethane, dimethyl sulfoxide, N,N-dimethylformamide, second
One of acetoacetic ester and butyl acetate are a variety of.Glycol (phenol) sodium compound citing include but is not limited to ethylene glycol sodium,
Hydroquinone sodium etc..
Following synthesis step can be used in the solid fireproof polymer as shown in formula (II) of the above-mentioned offer of the embodiment of the present invention
It is prepared:
It is separately added into cyclotrinitrile phosphide and solvent into three-necked flask, under the conditions of -20 DEG C -20 DEG C, is burnt to three mouthfuls
It is slowly added to alkene alcohol (phenol) sodium compound in bottle, is stirred to react at 25 DEG C -60 DEG C 6-48 hours, is filtered, is dried under reduced pressure, obtains
Corresponding monomeric olefin compound.Then above-mentioned corresponding monomeric olefin compound is dissolved in the solution containing initiator, 50
It is polymerize under the conditions of DEG C -120 DEG C, the solid fireproof polymer that above-mentioned logical formula (II) indicates is obtained by dissolution-sedimentation.
Wherein, the cyclotrinitrile phosphide is depending on the molecular structure of specific solid fireproof polymer to be prepared,
Including but not limited to hexachlorocyclotriph,sphazene, three phosphonitrile of hexafluoro ring, three phosphonitrile of ethyoxyl (five fluorine) ring, three phosphorus of phenoxy group (five fluorine) ring
Nitrile etc..The solvent includes but is not limited to ethane, hexamethylene, methylene chloride, chloroform, ether, petroleum ether, benzene, toluene, chlorine
Benzene, fluorobenzene, acetone, acetonitrile, methanol, ethyl alcohol, tetrahydrofuran, nitromethane, dimethyl sulfoxide, N,N-dimethylformamide, second
One of acetoacetic ester and butyl acetate are a variety of.Alkene alcohol (phenol) the sodium compound citing includes but is not limited to vinyl alcohol
Sodium, ethylene Pyrogentisinic Acid's sodium etc..The initiator includes azo-initiator, organic peroxy class initiator, inorganic peroxy initiator
And oxidation-reduction initiator, specifically, initiator citing includes but is not limited to azodiisobutyronitrile (AIBN), peroxidating two
Benzoyl (BPO), potassium peroxydisulfate, hydrogen peroxide-frerrous chloride etc..
The embodiment of the invention also provides a kind of lithium secondary battery electrode pieces, including collector and setting are in the collection
Electrode active material layers on fluid include the above-mentioned solid fireproof polymerization of the embodiment of the present invention in the electrode active material layers
Object.
In embodiment of the present invention, the solid fireproof polymer accounts for the 0.1%- of the electrode active material layers gross mass
20%, it further can be 1%-10%, 2%-8%.
In embodiment of the present invention, the solid fireproof polymer is graininess or powdered, and partial size is 0.01 μm -10
μm；The solid fireproof polymer is dispersed in the electrode active material layers.
In embodiment of the present invention, the lithium secondary battery electrode piece includes cathode plate for lithium secondary battery pole piece or the secondary electricity of lithium
Pond cathode pole piece.
When the lithium secondary battery electrode piece be cathode plate for lithium secondary battery pole piece when, collector can be it is existing it is conventional just
Pole collector, such as aluminium foil, electrode active material layers include positive electrode active materials, conductive agent and binder, the positive-active material
Material can be existing conventional material, such as cobalt acid lithium (LiCoO2)；The conductive agent and binder can also be existing common kind
Class, conductive agent can be super P, and binder can be Kynoar (PVDF).
Cathode plate for lithium secondary battery pole piece of the present invention can be used under type such as and prepare: weigh bonding by certain mass proportion
Agent, conductive agent, solid fireproof polymer and positive electrode active materials, are added sequentially in organic solvent, are thoroughly mixed uniformly,
Slurry is coated on plus plate current-collecting body, the cathode plate for lithium secondary battery pole piece is made in drying, cold pressing, cutting.Wherein, You Jirong
Agent can be, but not limited to be N-Methyl pyrrolidone (NMP).
When the lithium secondary battery electrode piece is lithium secondary battery anode pole piece, collector can be existing conventional bear
Pole collector, such as copper foil, electrode active material layers include negative electrode active material, conductive agent and binder, the negative electrode active material
Material can be existing conventional material, such as graphite；The conductive agent and binder can also be existing common type, and conductive agent can
To be acetylene black, binder can be sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR).
Lithium secondary battery anode pole piece of the present invention can be used under type such as and prepare: weigh bonding by certain mass proportion
Agent, conductive agent, solid fireproof polymer and negative electrode active material, are added sequentially in solvent, are thoroughly mixed uniformly, will starch
Material is coated on negative current collector, and the lithium secondary battery anode pole piece is made in drying, cold pressing, cutting.Wherein, solvent can with but
It is not limited to deionized water.
Lithium secondary battery electrode piece provided in an embodiment of the present invention has excellent flame retardant property, can effectively improve battery
Safety and guarantee battery chemical property performance.
The embodiment of the invention also provides a kind of diaphragm, the diaphragm includes septum body and is set to the septum body
The flame-retardant layer on one or both sides surface, the material of the flame-retardant layer include the above-mentioned solid fireproof polymer and bonding of the present invention
Agent.
In embodiment of the present invention, in the flame-retardant layer, the mass ratio of the solid fireproof polymer and the binder
For 1-100:1, further mass ratio is 50-95:1 or 70-80:1.
In embodiment of the present invention, the flame-retardant layer with a thickness of 0.1 μm -10 μm, further, with a thickness of 1 μm -8 μm,
3μm-6μm。
In embodiment of the present invention, the binder includes Kynoar (PVDF), polymethyl methacrylate
(PMMA), polytetrafluoroethylene (PTFE) (PTFE), Kynoar-hexafluoropropene (PVDF-HFP), polyacrylonitrile (PAN), polyimides
(PI), polyethylene glycol (PEG), Pluronic F-127 (PEO), poly-dopamine (PDA), sodium carboxymethylcellulose/butadiene-styrene rubber (CMC/
SBR), polyvinyl alcohol (PVA), polyacrylic acid (PAA), Lithium polyacrylate (LiPAA), polyvinylpyrrolidone (PVP), polylactic acid
(PLA), one of sodium alginate (SA), poly- p styrene sulfonic acid (PSS), poly- p styrene sulfonic acid lithium (LiPSS) and gelatin
Or it is a variety of.
In embodiment of the present invention, the septum body can be existing conventional business diaphragm, including but not limited to singly
The diaphragms such as PP/PP and three layer of layer PP (polypropylene), single layer PE (polyethylene), bilayer PP/PE, bilayer PP/PE/PP.
Diaphragm provided in an embodiment of the present invention can be used under type such as and prepare: matching by certain mass and polymerize solid fireproof
Object and binder are dissolved in organic solvent, are stirred into homogeneous solution, are coated uniformly in business septum body with scraper, system
Obtain diaphragm of the present invention.Wherein, organic solvent includes but is not limited to N-Methyl pyrrolidone (NMP).
Diaphragm provided in an embodiment of the present invention has excellent flame retardant property, is applied to lithium secondary battery, can be effective
It improves the safety of battery and guarantees the performance of the chemical property of battery.
The embodiment of the invention also provides a kind of lithium secondary batteries, including the above-mentioned lithium secondary battery electrode piece of the present invention
And/or the diaphragm that the present invention is above-mentioned.The i.e. described lithium secondary battery can select at least in anode pole piece, cathode pole piece and diaphragm
One mixes solid fireproof polymer provided in an embodiment of the present invention.The lithium secondary battery of the embodiment of the present invention, due to applying
Solid fireproof polymer with excellent fire-retardancy, thus there is high security, and since solid fireproof polymer is with solid
Body form exist, and with positive and negative pole material have favorable compatibility, thus it is possible to prevente effectively from electrolytic conductivity reduction, glue
The increase of degree, the generation of side reaction, so that lithium secondary battery has good cycle performance.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.
Embodiment 1
A kind of solid fireproof polymer, shown in molecular structural formula such as formula (A):
The preparation of the solid fireproof polymer (three phosphonitrile of polyethoxy (five fluorine) ring) of the present embodiment:
Three phosphonitrile of 2.0mol hexafluoro ring and 300mL acetonitrile are separately added into the three-necked flask of 500mL, under the conditions of 0 DEG C,
The acetonitrile mixture of 1.0mol ethylene glycol sodium is slowly added dropwise by constant pressure funnel, after being added dropwise, is stirred at 40 DEG C anti-
It answers 24 hours, filters, be dried under reduced pressure, obtain three phosphonitrile (A) of polyethoxy (five fluorine) ring, specifically n is 36.
The preparation of cathode plate for lithium secondary battery pole piece:
It is poly- for 2% Kynoar (PVDF), 2% conductive agent super P, 2% solid fireproof to weigh mass percentage
Close object A and 94% cobalt acid lithium (LiCoO2), it is added sequentially in N-Methyl pyrrolidone (NMP), is thoroughly mixed uniformly, it will
Slurry is coated in aluminum foil current collector, and drying, cuts the anode pole piece that the embodiment of the present invention 1 is made at cold pressing.
The preparation of lithium secondary battery:
Weighing mass percentage is 2%CMC, 3%SBR, 1% acetylene black and 94% graphite, is added sequentially to deionization
It in water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, obtained cathode pole piece is cut in drying, cold pressing；
Square electric cell is made in the anode pole piece of above-mentioned preparation, cathode pole piece and commercialization PP/PE/PP three-layer membrane, is used
1.0mol/L LiPF is perfused in polymer packaging6Electrolyte (EC, EMC, DEC, PC weight ratio are 35:25:25:15), through being melted into
Etc. the Soft Roll lithium secondary battery of 3.6Ah is made after techniques.
Embodiment 2
A kind of solid fireproof polymer, shown in molecular structural formula such as formula (B):
The solid fireproof polymer (B) of the present embodiment can be used the similar method of embodiment 1 and be prepared.
Three phosphonitrile of 1.0mol hexafluoro ring and 200mL acetonitrile are separately added into the three-necked flask of 500mL, under the conditions of 0 DEG C,
The acetonitrile mixture of 1.0mol hydroquinone sodium is slowly added dropwise by constant pressure funnel, after being added dropwise, is stirred at 60 DEG C
Reaction 48 hours, filtering, is dried under reduced pressure, obtains solid fireproof polymer (B), specifically n1、n2、n3、n4It is 12.
The preparation of cathode plate for lithium secondary battery pole piece:
It is poly- for 2% Kynoar (PVDF), 2% conductive agent super P, 2% solid fireproof to weigh mass percentage
Close object B and 94% cobalt acid lithium (LiCoO2), it is added sequentially in N-Methyl pyrrolidone (NMP), is thoroughly mixed uniformly, it will
Slurry is coated in aluminum foil current collector, and drying, cuts the anode pole piece that the embodiment of the present invention 2 is made at cold pressing.
The preparation of lithium secondary battery:
Weighing mass percentage is 2%CMC, 3%SBR, 1% acetylene black and 94% graphite, is added sequentially to deionization
It in water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, obtained cathode pole piece is cut in drying, cold pressing；
Square electric cell is made in the anode pole piece of above-mentioned preparation, cathode pole piece and commercialization PP/PE/PP three-layer membrane, is used
1.0mol/L LiPF is perfused in polymer packaging6Electrolyte (EC, EMC, DEC, PC weight ratio are 35:25:25:15), through being melted into
Etc. the Soft Roll lithium secondary battery of 3.6Ah is made after techniques.
Embodiment 3
A kind of solid fireproof polymer, shown in molecular structural formula such as formula (C):
The preparation of the solid fireproof polymer (polyethylene is to three phosphonitrile of phenoxy group (five fluorine) ring) of the present embodiment:
Three phosphonitrile of 1.0mol hexafluoro ring and 200mL acetonitrile are separately added into the three-necked flask of 500mL, under the conditions of 0 DEG C,
The acetonitrile mixture of 1.0mol ethylene Pyrogentisinic Acid's sodium is slowly added dropwise by constant pressure funnel, after being added dropwise, is stirred at 30 DEG C
Reaction 12 hours, filtering, is dried under reduced pressure, obtains corresponding monomer ethylene to three phosphonitrile of phenoxy group (five fluorine) ring.It then will be above-mentioned corresponding
Monomer ethylene is dissolved in the acetonitrile solution containing initiator (AIBN) three phosphonitrile of phenoxy group (five fluorine) ring, under the conditions of 60 DEG C
It is polymerize, polyethylene is obtained to three phosphonitrile (C) of phenoxy group (five fluorine) ring by dissolution-sedimentation, specifically n is about 108.
The preparation of cathode plate for lithium secondary battery pole piece:
It is poly- for 2% Kynoar (PVDF), 2% conductive agent super P, 2% solid fireproof to weigh mass percentage
Close object C and 94% cobalt acid lithium (LiCoO2), it is added sequentially in N-Methyl pyrrolidone (NMP), is thoroughly mixed uniformly, it will
Slurry is coated in aluminum foil current collector, and drying, cuts the anode pole piece that the embodiment of the present invention 3 is made at cold pressing.
The preparation of lithium secondary battery:
Weighing mass percentage is 2%CMC, 3%SBR, 1% acetylene black and 94% graphite, is added sequentially to deionization
It in water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, obtained cathode pole piece is cut in drying, cold pressing；
Square electric cell is made in the anode pole piece of above-mentioned preparation, cathode pole piece and commercialization PP/PE/PP three-layer membrane, is used
1.0mol/L LiPF is perfused in polymer packaging6Electrolyte (EC, EMC, DEC, PC weight ratio are 35:25:25:15), through being melted into
Etc. the Soft Roll lithium secondary battery of 3.6Ah is made after techniques.
Embodiment 4
The preparation of lithium secondary battery anode pole piece:
Weighing mass percentage is 1%CMC, 2%SBR, 1% acetylene black, 2% solid fireproof polymer A and 94% stone
Ink is added sequentially in deionized water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, dry, be cold-pressed,
Cut the cathode pole piece that the embodiment of the present invention 4 is made.
The preparation of lithium secondary battery:
Weighing mass percentage is 2% Kynoar (PVDF), 2% conductive agent super P and 96% cobalt acid lithium
(LiCoO2), it is added sequentially in N-Methyl pyrrolidone (NMP), is thoroughly mixed uniformly, slurry is coated on aluminium foil collection
On fluid, obtained anode pole piece is cut in drying, cold pressing；
Square electric cell is made in the anode pole piece of above-mentioned preparation, cathode pole piece and commercialization PP/PE/PP three-layer membrane, is used
1.0mol/L LiPF is perfused in polymer packaging6Electrolyte (EC, EMC, DEC, PC weight ratio are 35:25:25:15), through being melted into
Etc. the Soft Roll lithium secondary battery of 3.6Ah is made after techniques.
Embodiment 5
The preparation of lithium secondary battery anode pole piece:
Weighing mass percentage is 1%CMC, 2%SBR, 1% acetylene black, 2% solid fireproof polymer B and 94% stone
Ink is added sequentially in deionized water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, dry, be cold-pressed,
Cut the cathode pole piece that the embodiment of the present invention 5 is made.
The preparation of lithium secondary battery: with embodiment 4.
Embodiment 6
The preparation of lithium secondary battery anode pole piece:
Weighing mass percentage is 1%CMC, 2%SBR, 1% acetylene black, 2% solid fireproof polymer C and 94% stone
Ink is added sequentially in deionized water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, dry, be cold-pressed,
Cut the cathode pole piece that the embodiment of the present invention 6 is made.
The preparation of lithium secondary battery: with embodiment 4.
Embodiment 7
The preparation of diaphragm:
Weighing mass percentage is that 90% solid fireproof polymer A and 10%PVDF is dissolved in NMP, is stirred into equal
Even solution is coated uniformly on the two sides of PP diaphragm with 1 μm of scraper, and the diaphragm of the embodiment of the present invention 7 is made.
The preparation of lithium secondary battery:
Weighing mass percentage is 2% Kynoar (PVDF), 2% conductive agent super P and 96% cobalt acid lithium
(LiCoO2), it is added sequentially in N-Methyl pyrrolidone (NMP), is thoroughly mixed uniformly, slurry is coated on aluminium foil collection
On fluid, obtained anode pole piece is cut in drying, cold pressing；
Weighing mass percentage is 2%CMC, 3%SBR, 1% acetylene black and 94% graphite, is added sequentially to deionization
It in water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, obtained cathode pole piece is cut in drying, cold pressing；
Square electric cell is made in the anode pole piece of above-mentioned preparation, cathode pole piece and the present embodiment diaphragm, using polymer packet
1.0mol/L LiPF is perfused in dress6Electrolyte (EC, EMC, DEC, PC weight ratio are 35:25:25:15), after the techniques such as chemical conversion
The Soft Roll lithium secondary battery of 3.6Ah is made.
Embodiment 8
The preparation of diaphragm:
Weighing mass percentage is that 90% solid fireproof polymer B and 10%PVDF are dissolved in NMP, is stirred into equal
Even solution is coated uniformly on the two sides of PP diaphragm with 1 μm of scraper, and the diaphragm of the embodiment of the present invention 8 is made.
The preparation of lithium secondary battery: with embodiment 7.
Embodiment 9
The preparation of diaphragm:
Weighing mass percentage is that 90% solid fireproof polymer C and 10%PVDF is dissolved in NMP, is stirred into equal
Even solution is coated uniformly on the two sides of PP diaphragm with 1 μm of scraper, and the diaphragm of the embodiment of the present invention 9 is made.
The preparation of lithium secondary battery: with embodiment 7.
Comparative example 1
The preparation of lithium secondary battery: weighing mass percentage is 2% Kynoar (PVDF), 2% conductive agent super
P and 96% cobalt acid lithium (LiCoO2), it is added sequentially in N-Methyl pyrrolidone (NMP), is thoroughly mixed uniformly, by slurry
It is coated in aluminum foil current collector, obtained anode pole piece is cut in drying, cold pressing；
Weighing mass percentage is 2%CMC, 3%SBR, 1% acetylene black and 94% graphite, is added sequentially to deionization
It in water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, obtained cathode pole piece is cut in drying, cold pressing；
Square electric cell is made in the anode pole piece of above-mentioned preparation, cathode pole piece and commercialization PP/PE/PP three-layer membrane, is used
1.0mol/L LiPF is perfused in polymer packaging6Electrolyte (EC, EMC, DEC, PC weight ratio are 35:25:25:15), through being melted into
Etc. the Soft Roll lithium secondary battery of 3.6Ah is made after techniques.
Comparative example 2
The preparation of lithium secondary battery: weighing mass percentage is 2% Kynoar (PVDF), 2% conductive agent super
P and 96% cobalt acid lithium (LiCoO2), it is added sequentially in N-Methyl pyrrolidone (NMP), is thoroughly mixed uniformly, by slurry
It is coated in aluminum foil current collector, obtained anode pole piece is cut in drying, cold pressing；
Weighing mass percentage is 2%CMC, 3%SBR, 1% acetylene black and 94% graphite, is added sequentially to deionization
It in water, is thoroughly mixed uniformly, slurry is coated in copper foil current collector, obtained cathode pole piece is cut in drying, cold pressing；
It weighs and is dissolved in NMP with the PVDF of 7 equivalent of embodiment, be stirred into homogeneous solution, uniformly coated with 1 μm of scraper
On the two sides of PP diaphragm, the diaphragm of comparative example 2 of the present invention is made；
Square electric cell is made in the anode pole piece, cathode pole piece and diaphragm of above-mentioned preparation, using polymer packaging, perfusion
1.0mol/L LiPF6Electrolyte (EC, EMC, DEC, PC weight ratio are 35:25:25:15), is made after the techniques such as chemical conversion
The Soft Roll lithium secondary battery of 3.6Ah.
Effect example
To provide powerful support for technical solution bring beneficial effect of the embodiment of the present invention, following test is provided:
(1) safety of lithium secondary battery can be tested
Use diameter for the high temperature resistant steel needle of 3-8mm, with the speed of 10-40mm/s to 1-9 of the embodiment of the present invention and comparison
Lithium secondary battery prepared by example 1-2 carries out needle thorn experiment, and whether record battery core is on fire and explodes, and the results are shown in Table 1.
(2) lithium secondary battery cycle performance is tested
Lithium secondary battery prepared by 1-9 of the embodiment of the present invention and comparative example 1-2 is carried out with 1.0/1.0C charge-discharge magnification
Charge and discharge cycles test, graphite/LiCoO2The voltage range of battery is 3.0-4.4V, and capacity retention ratio of the record after 500 weeks is surveyed
Test result is listed in table 1.In addition, Fig. 1, Fig. 2, Fig. 3, Fig. 4 are respectively the embodiment of the present invention 1, embodiment 9, comparative example 1 and comparative example
Preceding 100 weeks cyclic curves of 2 lithium secondary battery.
1 embodiment 1-9 of table and comparative example 1-2 security performance and cycle performance test result
It can know from 1 test result of table, the battery progress needle thorn experiment in 1-9 of the embodiment of the present invention does not occur on fire
And explosion, and the battery progress needle thorn experiment generation in comparative example 1-2 is on fire, that is, shows the solid resistance containing the embodiment of the present invention
The battery for firing polymer has higher flame resistance, improves the safety of lithium secondary battery.In addition, simultaneously, testing and tying from table 1
The cyclic curve figure of fruit and Fig. 1-4 it can also be seen that, compare comparative example 1-2, the battery in 1-9 of the embodiment of the present invention has higher
Capacity retention ratio, cycle performance is more excellent, and this is mainly due to the solid fireproof polymer of the embodiment of the present invention not to dissolve in lithium two
The electrolyte of primary cell, it can stir slurry with positive and negative pole material and be prepared by mixing into positive and negative anodes pole piece, or be existed by adhesive coated
Membrane surface can overcome conventional method that fire retardant is directly appended in electrolyte the negative effect caused by battery performance.
The solid fireproof polymer of the embodiment of the present invention, not only without the performance of deterioration electrolyte, but also with positive and negative pole material with good
Good compatibility, improves the chemical property of battery, has wide application market.
Claims (17)
1. a kind of solid fireproof polymer, which is characterized in that the solid fireproof polymer includes containing three phosphonitrile structure of ring
Repetitive unit is polymerized by the monomer containing three phosphonitrile structure of ring by chemical bond grafting, the solid fireproof polymer
Shown in general formula such as formula (I) or formula (II),
In formula (I), the X is selected from alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, alkenylene, halogenated sub- alkene
Base, halogenated sub- alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group, replaces phosphoric acid Asia ester at sub- alkenyloxy group
Base, substituted imides base, replace sulfimide base in any one；The R1、R2、R3、R4It is respectively selected from fluorine, chlorine, bromine, alkane
Base, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy group, haloalkenyloxy, aryl, halogenated aryl,
Any one in aryloxy group, haloaryloxy；
In formula (II), the Y is selected from oxygen, sulphur, alkylidene, halogeno alkylen, alkylene oxide group, halo alkyleneoxy, alkenylene, halogen
For alkenylene, sub- alkenyloxy group, halogenated sub- alkenyloxy group, arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group, replace phosphorus
Sour Asia ester group, substituted imides base replace any one in sulfimide base；The R1’、R2’、R3’、R4’、R5' select respectively
From fluorine, chlorine, bromine, alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy group, haloalkenyloxy, virtue
Base, halogenated aryl, aryloxy group, any one in haloaryloxy.
2. solid fireproof polymer as described in claim 1, which is characterized in that in the X and the Y, the alkylidene, halogen
Carbon atom number for alkylidene, alkylene oxide group, halo alkyleneoxy is 1-20；The alkenylene, haloalkenediyl, sub- alkene oxygen
Base, halogenated sub- alkenyloxy group carbon atom number be 2-20；The arlydene, halogenated arlydene, sub- aryloxy group, halogenated sub- aryloxy group
Carbon atom number is 6-20；It is described to replace phosphoric acid Asia ester group, substituted imides base and replace the substituent group in sulfimide base
Carbon atom number is 1-20.
3. solid fireproof polymer as described in claim 1, which is characterized in that in the X and the Y, the halogenated alkylene
Base, halo alkyleneoxy, haloalkenediyl, halogenated sub- alkenyloxy group, halogenated arlydene, the halogen in halogenated sub- aryloxy group include
Fluorine, chlorine, bromine, iodine, it is described halogenated for perhalogeno or partially halogenated.
4. solid fireproof polymer as described in claim 1, which is characterized in that the R1、R2、R3、R4、R1’、R2’、R3’、R4’
And R5' in, the alkyl, halogenated alkyl, alkoxy, halogenated alkoxy carbon atom number be 1-20；The alkenyl, haloalkene
Base, alkenyloxy group, the carbon atom number of haloalkenyloxy are 2-20；The aryl, halogenated aryl, aryloxy group, haloaryloxy carbon
Atomicity is 6-20.
5. solid fireproof polymer as described in claim 1, which is characterized in that the R1、R2、R3、R4、R1’、R2’、R3’、R4’
And R5' in, the halogenated alkyl, halogenated alkoxy, halogenated alkenyl, haloalkenyloxy, halogenated aryl, the halogen in haloaryloxy
Element includes fluorine, chlorine, bromine, iodine, described halogenated for perhalogeno or partially halogenated.
6. solid fireproof polymer as described in claim 1, which is characterized in that in the formula (I), n 2-1000.
7. solid fireproof polymer as described in claim 1, which is characterized in that in the formula (II), n 2-1000.
8. solid fireproof polymer as described in claim 1, which is characterized in that the X and Y be respectively selected from methylene,
Ethylidene, propylidene, isopropylidene, butylidene, Asia 1- cyclobutenyl, perfluor replace Aden's alkyl, difluoro to replace inferior ethoxyl, first
Base phenylene, vinyl phenylene, fluoro substituted phenylen, methyl acid phosphate Asia ester group, trifluoroethyl phosphoric acid Asia ester group, sub- acetimide
Any one in base and difluoro methylene sulfimide base.
9. a kind of lithium secondary battery electrode piece, which is characterized in that including collector and the electrode being arranged on the collector
Active material layer includes such as the described in any item solid fireproof polymer of claim 1-8 in the electrode active material layers.
10. lithium secondary battery electrode piece as claimed in claim 9, which is characterized in that the solid fireproof polymer accounts for described
The 0.1%-20% of electrode active material layers gross mass.
11. lithium secondary battery electrode piece as claimed in claim 9, which is characterized in that the solid fireproof polymer uniformly divides
It dissipates in the electrode active material layers.
12. lithium secondary battery electrode piece as claimed in claim 9, which is characterized in that the lithium secondary battery electrode piece includes
Cathode plate for lithium secondary battery pole piece or lithium secondary battery anode pole piece.
13. a kind of diaphragm, which is characterized in that the diaphragm includes septum body and is set to the septum body one or both sides
The flame-retardant layer on surface, the material of the flame-retardant layer include such as the described in any item solid fireproof polymer of claim 1-8 and glue
Tie agent.
14. diaphragm as claimed in claim 13, which is characterized in that in the flame-retardant layer, the solid fireproof polymer and institute
The mass ratio for stating binder is 1-100:1.
15. diaphragm as claimed in claim 13, which is characterized in that the flame-retardant layer with a thickness of 0.1 μm -10 μm.
16. diaphragm as claimed in claim 13, which is characterized in that the binder includes Kynoar, polymethyl
Sour methyl esters, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropene, polyacrylonitrile, polyimides, polyethylene glycol, Pluronic F-127,
Poly-dopamine, sodium carboxymethylcellulose/butadiene-styrene rubber, polyvinyl alcohol, polyacrylic acid, Lithium polyacrylate, polyvinylpyrrolidone,
One of polylactic acid, sodium alginate, poly- p styrene sulfonic acid, poly- p styrene sulfonic acid lithium and gelatin are a variety of.
17. a kind of lithium secondary battery, which is characterized in that including the described in any item lithium secondary battery electrode pieces of claim 9-12
And/or the described in any item diaphragms of claim 13-16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711444931.0A CN109970981B (en) | 2017-12-27 | 2017-12-27 | Solid flame-retardant polymer, electrode plate, diaphragm and lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711444931.0A CN109970981B (en) | 2017-12-27 | 2017-12-27 | Solid flame-retardant polymer, electrode plate, diaphragm and lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109970981A true CN109970981A (en) | 2019-07-05 |
| CN109970981B CN109970981B (en) | 2022-04-12 |
Family
ID=67071570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711444931.0A Active CN109970981B (en) | 2017-12-27 | 2017-12-27 | Solid flame-retardant polymer, electrode plate, diaphragm and lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109970981B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110581248A (en) * | 2019-08-23 | 2019-12-17 | 中南大学 | Lithium-sulfur battery and composite diaphragm thereof |
| CN110698586A (en) * | 2019-10-14 | 2020-01-17 | 北京卫蓝新能源科技有限公司 | Lithium battery positive electrode additive and preparation method thereof |
| CN111900365A (en) * | 2020-09-04 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN112331856A (en) * | 2020-11-03 | 2021-02-05 | 华东理工大学华昌聚合物有限公司 | Lithium ion battery electrode binder and preparation method and application thereof |
| CN112582693A (en) * | 2020-12-07 | 2021-03-30 | 界首市天鸿新材料股份有限公司 | Flame-retardant treatment method for polyolefin diaphragm of lithium battery |
| CN115084646A (en) * | 2022-06-24 | 2022-09-20 | 江西师范大学 | Cyclotriphosphazene-based flame-retardant polymer electrolyte and preparation method and application thereof |
| CN115832625A (en) * | 2021-12-02 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Flame retardant and secondary battery comprising same |
| US11985841B2 (en) | 2020-12-07 | 2024-05-14 | Oti Lumionics Inc. | Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05286988A (en) * | 1992-04-14 | 1993-11-02 | Idemitsu Petrochem Co Ltd | Curable phosphazene compound, its production and cured body thereof |
| JP2003147050A (en) * | 2001-11-09 | 2003-05-21 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| CN1725547A (en) * | 2004-07-21 | 2006-01-25 | 上海比亚迪有限公司 | Lithium ion secondary battery |
| CN101252189A (en) * | 2008-03-21 | 2008-08-27 | 北京理工大学 | Method for improving lithium ion battery thermal stabilization through doping |
| JP2013075836A (en) * | 2011-09-29 | 2013-04-25 | Fushimi Pharm Co Ltd | Flame retardant resin composition |
| CN103151513A (en) * | 2013-03-13 | 2013-06-12 | 山东神工海特电子科技有限公司 | High-performance ternary power battery and preparation method of high-performance ternary power battery |
| CN106946937A (en) * | 2016-01-07 | 2017-07-14 | 广东广山新材料股份有限公司 | A kind of phosphazene compound of cyano-containing, preparation method and purposes |
| CN107021986A (en) * | 2017-05-03 | 2017-08-08 | 江苏宁龙高科新材料有限公司 | A kind of phenoxy phosphazene fire retardant and preparation method thereof |
-
2017
- 2017-12-27 CN CN201711444931.0A patent/CN109970981B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05286988A (en) * | 1992-04-14 | 1993-11-02 | Idemitsu Petrochem Co Ltd | Curable phosphazene compound, its production and cured body thereof |
| JP2003147050A (en) * | 2001-11-09 | 2003-05-21 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| CN1725547A (en) * | 2004-07-21 | 2006-01-25 | 上海比亚迪有限公司 | Lithium ion secondary battery |
| CN101252189A (en) * | 2008-03-21 | 2008-08-27 | 北京理工大学 | Method for improving lithium ion battery thermal stabilization through doping |
| JP2013075836A (en) * | 2011-09-29 | 2013-04-25 | Fushimi Pharm Co Ltd | Flame retardant resin composition |
| CN103151513A (en) * | 2013-03-13 | 2013-06-12 | 山东神工海特电子科技有限公司 | High-performance ternary power battery and preparation method of high-performance ternary power battery |
| CN106946937A (en) * | 2016-01-07 | 2017-07-14 | 广东广山新材料股份有限公司 | A kind of phosphazene compound of cyano-containing, preparation method and purposes |
| CN107021986A (en) * | 2017-05-03 | 2017-08-08 | 江苏宁龙高科新材料有限公司 | A kind of phenoxy phosphazene fire retardant and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| ANDRIES P. JEKEL ETAL: ""Syntheses and Structures of Precursors in the Polycondensation of Hexachlorocyclotriphosphazene and Hydroquinone"", 《INORGANICA CHIMICA ACTA》 * |
| DANIEL HERNANDEZ-RUBIO ETAL: ""Synthesis and polymerization of styryloxyclophosphazenen derivatives"", 《POLYMERPREPRINTS》 * |
| HO LIM ETAL: ""Thermally stable and flame retardant low dielectric polymers based on cyclotriphosphazenes"", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110581248A (en) * | 2019-08-23 | 2019-12-17 | 中南大学 | Lithium-sulfur battery and composite diaphragm thereof |
| CN110581248B (en) * | 2019-08-23 | 2021-02-26 | 中南大学 | Lithium-sulfur battery and composite diaphragm thereof |
| CN110698586A (en) * | 2019-10-14 | 2020-01-17 | 北京卫蓝新能源科技有限公司 | Lithium battery positive electrode additive and preparation method thereof |
| CN110698586B (en) * | 2019-10-14 | 2022-07-12 | 北京卫蓝新能源科技有限公司 | Lithium battery positive electrode additive and preparation method thereof |
| CN111900365A (en) * | 2020-09-04 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN112331856A (en) * | 2020-11-03 | 2021-02-05 | 华东理工大学华昌聚合物有限公司 | Lithium ion battery electrode binder and preparation method and application thereof |
| CN112582693A (en) * | 2020-12-07 | 2021-03-30 | 界首市天鸿新材料股份有限公司 | Flame-retardant treatment method for polyolefin diaphragm of lithium battery |
| CN112582693B (en) * | 2020-12-07 | 2021-10-22 | 界首市天鸿新材料股份有限公司 | Flame-retardant treatment method for polyolefin diaphragm of lithium battery |
| US11985841B2 (en) | 2020-12-07 | 2024-05-14 | Oti Lumionics Inc. | Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating |
| CN115832625A (en) * | 2021-12-02 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Flame retardant and secondary battery comprising same |
| CN115084646A (en) * | 2022-06-24 | 2022-09-20 | 江西师范大学 | Cyclotriphosphazene-based flame-retardant polymer electrolyte and preparation method and application thereof |
| CN115084646B (en) * | 2022-06-24 | 2023-05-12 | 江西师范大学 | Cyclotriphosphazene-based flame-retardant polymer electrolyte, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109970981B (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109970981A (en) | A kind of solid fireproof polymer, electrode slice, diaphragm and lithium secondary battery | |
| Liu et al. | In situ polymerization for integration and interfacial protection towards solid state lithium batteries | |
| US6168885B1 (en) | Fabrication of electrodes and devices containing electrodes | |
| KR102408332B1 (en) | Conductive resin composition and electrode composition for electrode, electrode and lithium ion battery using same | |
| CN109103488B (en) | Polymer sodium battery and preparation method and application thereof | |
| CN106058317A (en) | Lithium-ion battery electrolyte, lithium-ion battery and electronic instrument | |
| Zhu et al. | In situ 3D crosslinked gel polymer electrolyte for ultra-long cycling, high-voltage, and high-safety lithium metal batteries | |
| CN103155246A (en) | Electrode for nonaqueous secondary batteries, nonaqueous secondary battery comprising same, and battery | |
| WO2006109443A1 (en) | Nonaqueous electrolyte solution for battery and nonaqueous electrolyte secondary battery comprising same | |
| JPH10283839A (en) | Polymer solid electrolyte, production thereof, and lithium secondary battery using thereof | |
| CN109935904A (en) | A kind of electrolysis additive, lithium secondary cell electrolyte and lithium secondary battery | |
| CN111864258A (en) | Solid composite electrolyte membrane, method for producing same, and polymer secondary battery | |
| CN110034327A (en) | A kind of list lithium ion conducting polymer lithium salts, lithium secondary cell electrolyte and lithium secondary battery | |
| JP2005142141A (en) | Organic electrolyte and lithium battery using the same | |
| CN108615941A (en) | A kind of additive of anti-thermal runaway and its application in secondary lithium metal | |
| JP5633817B2 (en) | Non-aqueous electrolyte for electric device and secondary battery using the same | |
| JP5093992B2 (en) | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery provided with the same | |
| CN114373986A (en) | Polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery | |
| US7097943B2 (en) | UV-cured multi-component polymer blend electrolyte, lithium secondary battery and their fabrication method | |
| CN115505115B (en) | Composition for preparing gel electrolyte, electrolyte and battery thereof | |
| CN106207122A (en) | Polymer Li-ion battery negative material and polymer Li-ion battery and electronic equipment | |
| CN110265702A (en) | Flame-retardant and overcharge-proof electrolyte additive and electrolyte containing additive | |
| JP2006286570A (en) | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery having it | |
| JP2872223B2 (en) | Vinyl acetate copolymer, gel polymer electrolyte composition containing the same, and lithium polymer secondary battery | |
| CN116706234B (en) | Layered ternary cathode material-adapted electrolyte, ternary lithium ion battery and preparation method thereof |
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 |