CN109830743A - Gel polymer electrolyte, lithium ion secondary battery and preparation method - Google Patents
Gel polymer electrolyte, lithium ion secondary battery and preparation method Download PDFInfo
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- CN109830743A CN109830743A CN201811451698.3A CN201811451698A CN109830743A CN 109830743 A CN109830743 A CN 109830743A CN 201811451698 A CN201811451698 A CN 201811451698A CN 109830743 A CN109830743 A CN 109830743A
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Abstract
The invention discloses a kind of gel polymer electrolyte, be by -30 DEG C~30 DEG C be liquid mixture, the high temperature polymerization at 45 DEG C~85 DEG C and formed；It is in terms of 100% by mixture quality, comprising: component A: accounting for 0.5%~5%, including at least one organic monomer containing a unsaturated double-bond；Component B: accounting for 0.01%~5%, including at least one crosslinking agent, and the crosslinking agent contains at least two unsaturated double-bonds；Component C: 0.0001%~1.55%, including at least one thermal initiator and/or at least one photoinitiator are accounted for；Component D: the liquid electrolyte of liquid lithium ionic cell, including organic solvent and lithium salts.Also disclose this method for preparing gel polymer electrolyte, lithium ion secondary battery and preparation method with this gel polymer electrolyte.Gel polymer electrolyte chemical property of the invention and stable electrochemical property improve the cycle life and high temperature resistance of lithium ion battery, have high security.
Description
Technical field
The present invention relates to the electrolyte of lithium ion battery, especially gel polymer electrolyte and preparation method thereof, and
Lithium ion secondary battery and preparation method thereof with the gel polymer electrolyte.
Background technique
Lithium ion battery due to its energy density is high, have extended cycle life and be environmentally friendly the advantages that and be widely used in
The digital products such as mobile phone, laptop, and be considered as electric car (EV) and hybrid vehicle (HEV)
Ideal power battery.
It is divided by electrolyte, lithium ion battery can be divided into liquid lithium ionic cell and polymer Li-ion electricity at present
Pond.Liquid lithium ionic cell has the advantages that high current charge-discharge, low temperature charge-discharge performance are good, but liquid electrolyte is easy
Leakage causes the safety problems such as burning, explosion.Polymer Li-ion battery is then not present safety caused by electrolyte leakage and asks
Topic, causes more and more extensive research and concern.Polymer dielectric includes gel polymer electrolyte and all solid state electrolysis
Matter, wherein all solid state electrolyte is mainly with plasma enhanced oxidation object (PEO) for representative, but its conductivity is extremely low, about
10-8s·cm-1, therefore hinder its application.
European patent application " Gel electrolyte including additives for rechargeable
Lithium battery, and rechargeable lithium battery including same " (publication number:
EP2400589A1, publication date: 2011-12-28) a kind of preparation of gel electrolyte is disclosed, which is contained by a variety of
The monomer of the carbonates of unsaturated double-bond, ethers and ketone is formed through initiator thermal polymerization.
U.S. Patent application " Polymer gel electrolyte and lithium battery employing
The same " (publication number: US6949318B2, publication date: 2005-09-27) discloses a kind of gel-form solid polymer electrolyte,
The polymer includes two-phase, and a phase is polyalcohols, and another phase is polyethylene glycol oxide, polymethacrylates, polyarylate, polypropylene
One of ester or in which several mixtures.
A kind of Chinese patent application " method for preparing gel polymer electrolyte " (publication number: CN1645662A, publication date
Phase: 2005-07-27) it also discloses about method for preparing gel polymer electrolyte.
The prior art disclosed above can obtain gel-like electrolyte, but its matrix is mainly polypropylene and its derivative
The chain copolymer of object, polycarbonate and its derivative is easy by having containing lithium salts therein under high temperature environment for a long time
Solvent corrosion, to reduce the cycle life of lithium battery.As physical polymer gel, it is easy to send out with temperature change
Raw reversible thermal decomposition variation, this is unfavorable for lithium battery and works under high temperature environment.
Summary of the invention
Goal of the invention: in view of the above-mentioned problems, an object of the present invention is to provide a kind of coagulating for polymer Li-ion battery
Xanthan polymer electrolyte has good high temperature resistance, mechanical strength, lithium ionic mobility, the second object of the present invention is to
A kind of this method for preparing gel polymer electrolyte is provided, the third object of the present invention is to provide a kind of with this gel
The lithium ion secondary battery of polymer dielectric, the fourth object of the present invention are to provide a kind of system of this lithium ion secondary battery
Preparation Method.
Technical solution: a kind of gel polymer electrolyte is by being the mixture of liquid at -30 DEG C~30 DEG C, 45
DEG C~85 DEG C at high temperature polymerization and formed；By the mixture quality be 100% in terms of, the mixture include following components and
Content:
Component A: including at least one organic monomer containing a unsaturated double-bond, the component A accounts for the mixture
0.5%~5%；The general formula of the organic monomer are as follows:
Wherein: R1, R2, R3, R4, R5, R6 are respectively that perhaps the part fluorine substitution of F or C1~C4 or whole fluorine take H
For alkyl, phenyl ring and hydroxyl；R7, R8 are respectively H or F；
Component B: including at least one crosslinking agent, the crosslinking agent contains at least two unsaturated double-bonds, the component B
Account for the 0.01%~5% of the mixture；
Component C: the mixture is accounted for including at least one thermal initiator and/or at least one photoinitiator, the component C
0.0001%~1.55%；
Component D: the liquid electrolyte of liquid lithium ionic cell, including organic solvent and lithium salts.
In component B: containing the crosslinking agent there are two unsaturated double-bond be, for example, styrene, vinyltoluene, divinylbenzene,
N, N'- methylene-bisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate etc.；Containing there are three
Or the crosslinking agent of four unsaturated double-bonds is, for example,
Deng.
In component C: photoinitiator can be free radical polymerization photoinitiator, e.g. 2- hydroxy-2-methyl -1- phenyl third
Ketone, 1- hydroxycyclohexyl phenyl ketone, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6-
Trimethylbenzoy-dipheny phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2- dimethylamino -2- benzyl
Base -1- [4- (4- morpholinyl) phenyl] -1- butanone, 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- third
Ketone, methyl benzoylformate etc. are also possible to Cationic photoinitiator, e.g. diaryl iodonium salt, triaryl iodine
Salt, alkyl salt compounded of iodine, isopropylbenzene cyclopentadienyl iron hexafluorophosphate etc.；Thermal initiator be, for example, azodiisobutyronitrile, azobisisoheptonitrile,
Azo-bis-iso-dimethyl, benzoyl peroxide, dilauroyl peroxide, cumyl peroxide, di-t-butyl peroxide, mistake
Aoxidize t-butyl perbenzoate etc..
In component D: liquid electrolyte must include organic solvent and lithium salts, can also include additive.Organic solvent must
It must simultaneously include the solvent of the solvent that polarity is larger and dielectric constant is big and low viscosity, therefore type of solvent is binary, ternary, four
Member so multicomponent solvent, e.g. ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate,
Dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, carbonic acid first isopropyl ester, carbonic acid first butyl ester, in 1,4- fourth
Ester, dimethyl-tetrahydrofuran, 1,2- dimethoxy-ethane, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, fluoroform
Base ethylene carbonate, dimethyl sulfoxide, sulfolane, 4- methyl-1,3- butyrolactone, propane sultone, ethylene sulfite, contracting two
Glycol dimethyl ether, contracting triethylene glycol dimethyl ether etc..Content of the lithium salts in liquid electrolyte is 0.7mol/l~1.6mol/l,
E.g. LiClO4、LiPF6、LiBF4、LiODFB、LiFSI、 LiTFSi、LiCF3SO3、LiN(CF3SO2)2、LiB(C2O4)2、
LiBF2C2O4It is at least one of.Additive choose whether as needed using, such as use, e.g. VC, 1,3-PS,
LiBOB、VEC、VES、ES、PES、MMDS、DTD、FEC、LiPO2F2, SN, AND, TMSB, TMSP, TMSPi, diphenyl difluoro silicon
Alkane, three (2,2,2- trifluoroethyl) phosphite esters, 4- propyl sulfuric acid vinyl ester, three (2,2,2- trifluoroethyl) phosphite esters, cyanogen
Methyl acid phosphate diethylester etc. is known in the art at least one of, and mass content of the additive in liquid electrolyte is
0.01%~10%.
A kind of above-mentioned method for preparing gel polymer electrolyte, in drying nitrogen protection atmosphere, -30 DEG C~30 DEG C
At a temperature of prepare the mixture, then carry out gel polymerisation reaction, 40 DEG C~85 DEG C of reaction temperature, the reaction time 1.5~
96h。
A kind of lithium ion secondary battery includes anode, cathode, diaphragm and above-mentioned gel polymer electrolyte.
Further, above-mentioned lithium ion secondary battery, the anode, cathode, diaphragm, at least one of surface
Coated with ceramic layer, at least one metal oxide is contained in ceramic material.Due to the d of metal cation in metal oxide
Electronic shell is easy to lose or obtain electronics, has stronger redox property, therefore the ceramic layer has the work of catalytic polymerization
With can allow component A and B that polymerization reaction occurs and generate high molecular polymer, and ultimately form the chemically polymerization of gel electrolyte
Object matrix.
A kind of preparation method of above-mentioned lithium ion secondary battery, comprising the following steps:
Step 1: the mixture is prepared at a temperature of drying nitrogen protection atmosphere, -30 DEG C~30 DEG C；Positive, negative
Coated ceramic layer on pole, at least one of surface of diaphragm prepares lithium ion battery and does battery core；
Step 2: at a temperature of drying nitrogen protection atmosphere, -30 DEG C~30 DEG C, the mixture is injected into lithium ion
Battery seals after doing battery core；
Step 3: by after fluid injection battery core carry out gel polymerisation reaction, 40 DEG C~85 DEG C of reaction temperature, the reaction time 1.5
~96h.
The utility model has the advantages that compared with prior art, the invention has the advantages that
1, the crosslinking agent that the gel polymer electrolyte introduces, so that the matrix of the gel polymer electrolyte formed is to change
The property learned macromolecule matrix, chemical property and stable electrochemical property, improve the cycle life and high temperature resistant of lithium ion battery
Performance；
2, principle of displacement of the lithium ion in the gel polymer electrolyte and the principle of displacement one in liquid electrolyte
It causes, therefore the gel polymer electrolyte has higher lithium ionic mobility relative to other solid-phase electrolytes, it is solidifying using this
The lithium ion battery of xanthan polymer has and the consistent power-performance of lithium ion battery that uses liquid electrolyte.
3, since the gel polymer electrolyte is present in lithium ion battery in solid form, and the gelatin polymer
The matrix of electrolyte at high temperature will not depolymerization, therefore using the gelatin polymer lithium ion battery have high security.
Detailed description of the invention
Fig. 1 is the simple stainless steel inert electrode simulated battery that embodiment 1 injects gel polymer electrolyte, after dismantling
Photo；
Fig. 2 is the simple stainless steel inert electrode simulated battery that embodiment 1 injects gel polymer electrolyte, AC impedance
Test chart；
Fig. 3 is the simple stainless steel inert electrode simulated battery that embodiment 1 injects gel polymer electrolyte, cyclic voltammetric
Test chart；
Fig. 4 is that embodiment 1 injects the lithium ion secondary battery of gel polymer electrolyte and comparative example 1, embodiment 2 are injected
Lithium ion secondary battery and comparative example 2, the embodiment 3 of gel polymer electrolyte inject the lithium ion of gel polymer electrolyte
Secondary cell, 25 DEG C of 1CC1CD recycle 1000 weeks capacity retention ratio test charts；
Fig. 5 is that embodiment 1 injects the lithium ion secondary battery of gel polymer electrolyte and comparative example 1, embodiment 2 are injected
Lithium ion secondary battery and comparative example 2, the embodiment 3 of gel polymer electrolyte inject the lithium ion of gel polymer electrolyte
Secondary cell, 45 DEG C of 1CC1CD recycle 800 weeks capacity retention ratio test charts；
Fig. 6 is that embodiment 4 injects the lithium ion secondary battery of gel polymer electrolyte and comparative example 3, embodiment 5 are injected
4,25 DEG C of 1CC1CD of lithium ion secondary battery and comparative example of gel polymer electrolyte recycle 1000 weeks capacity retention ratios and test
Figure；
Fig. 7 is that embodiment 4 injects the lithium ion secondary battery of gel polymer electrolyte and comparative example 3, embodiment 5 are injected
4,45 DEG C of 1CC1CD of lithium ion secondary battery and comparative example of gel polymer electrolyte recycle 800 weeks capacity retention ratios and test
Figure.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is furture elucidated, these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Embodiment 1
A kind of gel polymer electrolyte is by being the mixture of liquid at -30 DEG C~30 DEG C, at 45 DEG C~80 DEG C
High temperature polymerization and formed.
By taking the mixture is 100g as an example, including following components and content:
Component A: a kind of organic monomer containing a unsaturated double-bond --- N,N-DMAA, 4g；
Component B: it is a kind of containing there are three or four unsaturated double-bonds crosslinking agent --- three acrylic acid propane front three alcohol esters,
1g；
Component C: a kind of thermal initiator --- 2,2- azodiisobutyronitriles, 0.01g；
Component D: the liquid electrolyte of liquid lithium ionic cell, 94.99g, consisting of: EC: EMC: DMC=1: 1: 1
(vol), LiPF6It is 1% (Weight) for 1mol/l, VC.It is denoted as La.
The raw material of the above components is through past water process, water content≤50ppm, HF≤100ppm.
Component A~D is added in the container under nitrogen protective atmosphere, 15 DEG C or so are uniformly mixed, by appropriate mixed liquor
It is injected separately into lithium ion secondary battery, simple stainless steel inert electrode simulated battery, in soft-package battery aluminium plastic bag.Battery seal
16~18h is first shelved afterwards, mixed liquor is made sufficiently to infiltrate inside battery pole piece and diaphragm, and battery is then placed in 45 DEG C of baking ovens again
Middle in-situ thermo-polymerization 60h, the mixture of liquid are converted into stable gel polymer electrolyte.Then: for simple stainless steel
Inert electrode simulated battery, (1) measure the frequency response of its AC impedance, and as shown in Fig. 3,25 DEG C of conductivity are about 9.2ms/
Cm, the conductivity is suitable with the liquid electrolyte at same temperature, is able to satisfy lithium battery to the conductivity demand of electrolyte, (2)
Cyclic voltammetric is measured, as shown in Fig. 2, oxygenolysis voltage is higher than 4.8V, illustrates the gel polymer electrolyte of the present embodiment
Oxidation resistent susceptibility is good, is able to satisfy the high voltage requirements of lithium battery；For aluminium plastic bag, aluminium plastic bag is dismantled, electrolyte is taken out and is placed in
It is squeezed between two sheet glass, whether there is or not leakages for observation.
Lithium ion secondary battery the preparation method comprises the following steps: dissolving binder in n-methyl-2-pyrrolidone in the present embodiment
(Kynoar), then by uniformly mixed positive electrode active materials (NCM523) and conductive agent (electrically conductive graphite and carbon black),
It is even to be dispersed in the n-methyl-2-pyrrolidone for having dissolved binder, anode sizing agent is obtained, which is uniformly coated on
Anode is made on aluminium foil；On the other hand, in deionized water evenly dispersed binder [(Kynoar or polytetrafluoroethylene (PTFE),
Or butadiene-styrene rubber)/butadiene-styrene rubber=2: 1 (mass ratio)] and modified graphite, negative electrode slurry is obtained, it is then that the negative electrode slurry is equal
Cathode is made in even be coated on copper foil；Using the diaphragm of two sides coated metal oxide ceramic layer.
Simple stainless steel inert electrode simulated battery the preparation method comprises the following steps: taking a fritter (circle) gel poly- in the present embodiment
Polymer electrolyte, which is placed between two stainless steel inert electrodes, is made into a simple battery.By La be used in the lithium of the present embodiment from
Sub- secondary cell obtains comparative example 1.
Embodiment 2
A kind of gel polymer electrolyte is by being the mixture of liquid at -30 DEG C~30 DEG C, at 45 DEG C~80 DEG C
High temperature polymerization and formed.
By taking the mixture is 100g as an example, including following components and content:
A kind of component A: organic monomer containing a unsaturated double-bond --- N, N- bis- (trifluoromethyl) acrylamide,
4g；
B: two kinds of component crosslinking agent --- triallyl phosphate, ethylene glycol dimethyl containing more than two unsaturated double-bonds
Acrylate, each 0.5g；
C: two kinds of thermal initiators of component --- 2,2- azodiisobutyronitriles, benzoyl peroxide, each 0.005g；
Component D: the liquid electrolyte of liquid lithium ionic cell, 94.99g, consisting of: EC: EMC: DMC=1: 1: 1
(vol), LiPF6It is 1% (Weight) for 1mol/l, VC 1%, LiFSI.It is denoted as Lb.
The raw material of the above components is through past water process, water content≤50ppm, HF≤100ppm.
Component A~D is added in the container under nitrogen protective atmosphere, 15 DEG C or so are uniformly mixed, by appropriate mixed liquor
It is injected separately into lithium ion secondary battery, in soft-package battery aluminium plastic bag.16~18h is first shelved after battery seal, fills mixed liquor
Sub-dip moistens inside battery pole piece and diaphragm, and battery is then placed in in-situ thermo-polymerization 40h in 60 DEG C of baking ovens, the mixture of liquid again
It is converted into stable gel polymer electrolyte.Then: for aluminium plastic bag, dismantling aluminium plastic bag, take out electrolyte and be placed in two glass
It is squeezed between glass piece, whether there is or not leakages for observation.
Lithium ion secondary battery the preparation method comprises the following steps: dissolving binder in n-methyl-2-pyrrolidone in the present embodiment
(Kynoar), then by uniformly mixed positive electrode active materials (NCM523) and conductive agent (electrically conductive graphite and carbon black),
It is even to be dispersed in the n-methyl-2-pyrrolidone for having dissolved binder, anode sizing agent is obtained, which is uniformly coated on
Anode is made on aluminium foil；On the other hand, in deionized water evenly dispersed binder [(Kynoar or polytetrafluoroethylene (PTFE),
Or butadiene-styrene rubber)/butadiene-styrene rubber=2: 1 (mass ratio)] and modified graphite, negative electrode slurry is obtained, it is then that the negative electrode slurry is equal
Cathode is made in even be coated on copper foil；Then in positive and negative anodes surface metallization oxide ceramic layer；Diaphragm uses Celgard
PP/PE composite membrane, with a thickness of 16~45 μm.
Lb is used in the lithium ion secondary battery of the present embodiment, obtains comparative example 2.
Embodiment 3
A kind of gel polymer electrolyte is by being the mixture of liquid at -30 DEG C~30 DEG C, at 45 DEG C~80 DEG C
High temperature polymerization and formed.
By taking the mixture is 100g as an example, including following components and content:
Component A: a kind of organic monomer containing a unsaturated double-bond --- N, N- dimethyl allene, 2g；
Component B: a kind of containing there are two the crosslinking agents of unsaturated double-bond --- ethyleneglycol dimethacrylate, 3g；
Component C: a kind of thermal initiator and a kind of photoinitiator --- azo-bis-iso-dimethyl, 2- hydroxy-2-methyl-
1- phenylacetone, each 0.005g；
Component D: the liquid electrolyte of liquid lithium ionic cell, 94.99g, consisting of: EC: EMC: DMC=1: 1: 1
(vol), LiPF6For 1mol/l.
The raw material of the above components is through past water process, water content≤50ppm, HF≤100ppm.
Component A~D is added in the container under nitrogen protective atmosphere, 15 DEG C or so are uniformly mixed, by appropriate mixed liquor
It is injected separately into lithium ion secondary battery, in soft-package battery aluminium plastic bag.16~18h is first shelved after battery seal, fills mixed liquor
Sub-dip moistens inside battery pole piece and diaphragm, battery is then placed in in-situ thermo-polymerization 10h in 70 DEG C of baking ovens again, while using ultraviolet
Light irradiates 10h, and the mixture of liquid is converted into stable gel polymer electrolyte.Then: for aluminium plastic bag, dismantling plastic-aluminum
Bag, taking-up electrolyte, which is placed between two sheet glass, to be squeezed, and whether there is or not leakages for observation.
Lithium ion secondary battery the preparation method comprises the following steps: dissolving binder in n-methyl-2-pyrrolidone in the present embodiment
(Kynoar), then by uniformly mixed positive electrode active materials (NCM523) and conductive agent (electrically conductive graphite and carbon black),
It is even to be dispersed in the n-methyl-2-pyrrolidone for having dissolved binder, anode sizing agent is obtained, which is uniformly coated on
Anode is made on aluminium foil；On the other hand, in deionized water evenly dispersed binder [(Kynoar or polytetrafluoroethylene (PTFE),
Or butadiene-styrene rubber)/butadiene-styrene rubber=2: 1 (mass ratio)] and modified graphite, negative electrode slurry is obtained, it is then that the negative electrode slurry is equal
Cathode is made in even be coated on copper foil；Using the diaphragm of two sides coated metal oxide ceramic layer.
Embodiment 4
A kind of gel polymer electrolyte is by being the mixture of liquid at -30 DEG C~30 DEG C, at 45 DEG C~80 DEG C
High temperature polymerization and formed.
By taking the mixture is 100g as an example, including following components and content:
Component A: a kind of organic monomer containing a unsaturated double-bond --- N, N- bis- ethyl carbonate acrylamide, 4g；
Component B: it is a kind of containing there are three or four unsaturated double-bonds crosslinking agent --- ethoxylated trimethylolpropane three
Acrylate, 1g；
Component C: a kind of thermal initiator and a kind of photoinitiator --- 2,2- azodiisobutyronitriles, diaryl iodonium salt, respectively
0.005g；
Component D: the liquid electrolyte of liquid lithium ionic cell, 94.98g, consisting of: EC: EMC: DMC=1: 1: 1
(vol), LiPF6For 1mol/l.It is denoted as Lc.
The raw material of the above components is through past water process, water content≤50ppm, HF≤100ppm.
Component A~D is added in the container under nitrogen protective atmosphere, 15 DEG C or so are uniformly mixed, by appropriate mixed liquor
It is injected separately into lithium ion secondary battery, in soft-package battery aluminium plastic bag.16~18h is first shelved after battery seal, fills mixed liquor
Sub-dip moistens inside battery pole piece and diaphragm, battery is then placed in 60 DEG C of baking ovens in-situ thermo-polymerization for 24 hours again, while using ultraviolet
Light irradiates 5h, and the mixture of liquid is converted into stable gel polymer electrolyte.Then: for aluminium plastic bag, aluminium plastic bag is dismantled,
Taking-up electrolyte, which is placed between two sheet glass, to be squeezed, and whether there is or not leakages for observation.
Lithium ion secondary battery the preparation method comprises the following steps: dissolving binder in n-methyl-2-pyrrolidone in the present embodiment
(Kynoar), then by uniformly mixed positive electrode active materials (NCM811) and conductive agent (electrically conductive graphite and carbon black),
It is even to be dispersed in the n-methyl-2-pyrrolidone for having dissolved binder, anode sizing agent is obtained, which is uniformly coated on
Anode is made on aluminium foil；On the other hand, in deionized water evenly dispersed binder [(Kynoar or polytetrafluoroethylene (PTFE),
Or butadiene-styrene rubber)/butadiene-styrene rubber=2: 1 (mass ratio)] and modified graphite, negative electrode slurry is obtained, it is then that the negative electrode slurry is equal
Cathode is made in even be coated on copper foil；Using the diaphragm of two sides coated metal oxide ceramic layer.
Lc is used in the lithium ion secondary battery of the present embodiment, obtains comparative example 3.
Embodiment 5
A kind of gel polymer electrolyte is by being the mixture of liquid at -30 DEG C~30 DEG C, at 45 DEG C~80 DEG C
High temperature polymerization and formed.
By taking the mixture is 100g as an example, including following components and content:
A: two kinds of organic monomers containing a unsaturated double-bond of component --- N, N- dimethylacrylamide, 2 (1- itrile groups
Methyl carbonic acid ester group) ethylene, each 2g；
Component B: it is a kind of containing there are three or four unsaturated double-bonds crosslinking agent --- three acrylic acid propane front three alcohol esters,
1g；
Component C: a kind of thermal initiator --- 2,2- azodiisobutyronitriles, 0.01g；
Component D: the liquid electrolyte of liquid lithium ionic cell, 94.99g, consisting of: EC: EMC: DMC=1: 1: 1
(vol), LiPF6For 1mol/l.
The raw material of the above components is through past water process, water content≤50ppm, HF≤100ppm.
Component A~D is added in the container under nitrogen protective atmosphere, 15 DEG C or so are uniformly mixed, by appropriate mixed liquor
It is injected separately into lithium ion secondary battery, in soft-package battery aluminium plastic bag.16~18h is first shelved after battery seal, fills mixed liquor
Sub-dip moistens inside battery pole piece and diaphragm, and battery is then placed in in-situ thermo-polymerization 10h in 80 DEG C of baking ovens, the mixture of liquid again
It is converted into stable gel polymer electrolyte.Then: for aluminium plastic bag, dismantling aluminium plastic bag, take out electrolyte and be placed in two glass
It is squeezed between glass piece, whether there is or not leakages for observation.
Lithium ion secondary battery the preparation method comprises the following steps: dissolving binder in n-methyl-2-pyrrolidone in the present embodiment
(Kynoar), then by uniformly mixed positive electrode active materials (NCM811) and conductive agent (electrically conductive graphite and carbon black),
It is even to be dispersed in the n-methyl-2-pyrrolidone for having dissolved binder, anode sizing agent is obtained, which is uniformly coated on
Anode is made on aluminium foil；On the other hand, in deionized water evenly dispersed binder [(Kynoar or polytetrafluoroethylene (PTFE),
Or butadiene-styrene rubber)/butadiene-styrene rubber=2: 1 (mass ratio)] and modified graphite, negative electrode slurry is obtained, it is then that the negative electrode slurry is equal
Cathode is made in even be coated on copper foil；Then in positive and negative anodes surface metallization oxide ceramic layer；Diaphragm uses Celgard
PP/PE composite membrane, with a thickness of 16~45 μm.
Lc is used in the lithium ion secondary battery of the present embodiment, obtains comparative example 4.
The simple stainless steel inert electrode simulated battery of injection gel polymer electrolyte is shown in attached drawing 1, after dismantling,
The gel state of electrolyte, yellowish color part are exactly the stable gel polymer electrolyte that the mixture of liquid is converted into.It is real
Apply the simple stainless steel inert electrode simulated battery of the gel polymer electrolyte injection embodiment 1 of example 2~5, situation after dismantling
It is almost the same.
By the obtained gel polymer electrolyte physical property of Examples 1 to 5, each self seeding gel polymer electrolyte
Aluminium plastic bag leakage situation, be classified as table 1:
Table 1
| Sample | Ionic conductivity (S/cm) | Aluminium plastic bag fluid seepage |
| Embodiment 1 | 9.02 | Nothing |
| Embodiment 2 | 8.93 | Nothing |
| Embodiment 3 | 8.78 | Nothing |
| Embodiment 4 | 9.46 | Nothing |
| Embodiment 5 | 7.65 | Nothing |
Embodiment 1 is injected into the lithium ion secondary battery of gel polymer electrolyte and comparative example 1, the injection of embodiment 2 are coagulated
Lithium ion secondary battery and comparative example 2, the embodiment 3 of xanthan polymer electrolyte inject the lithium ion two of gel polymer electrolyte
Primary cell, comparative cell performance are classified as table 2:
Table 2
In conjunction with table 2 and Fig. 4,5, it is seen that: using the battery of inventive gel polymer dielectric, there is more stable cyclicity
Can, while it is undamped in cryogenic property.
Embodiment 4 is injected into the lithium ion secondary battery of gel polymer electrolyte and comparative example 3, the injection of embodiment 5 are coagulated
The lithium ion secondary battery and comparative example 4 of xanthan polymer electrolyte, comparative cell performance are classified as table 3:
Table 3
In conjunction with table 3 and Fig. 6,7, it is seen that: using the battery of inventive gel polymer dielectric, there is more stable cyclicity
Can, while it is undamped in cryogenic property.
Claims (6)
1. a kind of gel polymer electrolyte, it is characterised in that: be by being the mixture of liquid at -30 DEG C~30 DEG C, 45
DEG C~85 DEG C at high temperature polymerization and formed；By the mixture quality be 100% in terms of, the mixture include following components and
Content:
Component A: including at least one organic monomer containing a unsaturated double-bond, the component A accounts for the mixture
0.5%~5%；The general formula of the organic monomer are as follows:
Wherein: R1, R2, R3, R4, R5, R6 are respectively that perhaps the part fluorine substitution of F or C1~C4 or whole fluorine replace hydrocarbon to H
Base, phenyl ring and hydroxyl；R7, R8 are respectively H or F；
Component B: including at least one crosslinking agent, the crosslinking agent contains at least two unsaturated double-bonds, and the component B accounts for described
The 0.01%~5% of mixture；
Component C: the mixture is accounted for including at least one thermal initiator and/or at least one photoinitiator, the component C
0.0001%~1.55%；
Component D: the liquid electrolyte of liquid lithium ionic cell, including organic solvent and lithium salts.
2. gel polymer electrolyte according to claim 1, it is characterised in that: the photoinitiator is free radical polymerization
Photoinitiator, Cationic photoinitiator.
3. a kind of any method for preparing gel polymer electrolyte of claim 1~2, it is characterised in that: in drying
Nitrogen protective atmosphere prepares the mixture at a temperature of -30 DEG C~30 DEG C, then carries out gel polymerisation reaction, reaction temperature
40 DEG C~85 DEG C, 1.5~96h of reaction time.
4. a kind of lithium ion secondary battery, it is characterised in that: include anode, cathode, diaphragm and any institute of claims 1 to 3
The gel polymer electrolyte stated.
5. lithium ion secondary battery according to claim 4, it is characterised in that: the anode, cathode, diaphragm, at least its
One of surface on be coated with ceramic layer, at least one metal oxide is contained in ceramic material.
6. a kind of preparation method of lithium ion secondary battery according to claim 5, it is characterised in that the following steps are included:
Step 1: the mixture is prepared at a temperature of drying nitrogen protection atmosphere, -30 DEG C~30 DEG C；Anode, cathode,
Coated ceramic layer on at least one of surface of diaphragm prepares lithium ion battery and does battery core；
Step 2: at a temperature of drying nitrogen protection atmosphere, -30 DEG C~30 DEG C, the mixture is injected into lithium ion battery
It is sealed after dry battery core；
Step 3: by after fluid injection battery core carry out gel polymerisation reaction, 40 DEG C~85 DEG C of reaction temperature, the reaction time 1.5~
96h。
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