CN110474089A - A kind of solid polymer electrolyte and all-solid lithium-ion battery - Google Patents
A kind of solid polymer electrolyte and all-solid lithium-ion battery Download PDFInfo
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- CN110474089A CN110474089A CN201910789858.3A CN201910789858A CN110474089A CN 110474089 A CN110474089 A CN 110474089A CN 201910789858 A CN201910789858 A CN 201910789858A CN 110474089 A CN110474089 A CN 110474089A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The present invention relates to technical field of lithium ion more particularly to a kind of solid polymer electrolyte and preparation method thereof and all-solid lithium-ion batteries.A kind of solid polymer electrolyte provided by the invention, including cross-linked polymer and lithium salts；The present invention also provides a kind of all-solid lithium-ion battery, including positive electrode, solid polymer electrolyte and negative electrode, the positive electrode includes plus plate current-collecting body and positive electrode；The positive electrode includes isocyanate crosslinking, positive active material；The negative electrode includes negative current collector and negative electrode material；The negative electrode material includes isocyanate crosslinking, negative electrode active material；The solid polymer electrolyte is solid polymer electrolyte, the solid polymer electrolyte conductivity with higher provided by the invention and preferable cycle performance described in above scheme.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of solid polymer electrolyte and all solid lithium from
Sub- battery.
Background technique
There is lithium battery long service life, power to withstand forces, and high, high/low temperature is adaptable, environmentally protective, memory-less effect
And the advantages that fast charging and discharging.1991, Sony successfully developed commercial lithium battery.Since the performance of lithium battery is excellent
More, it is widely applied in the handheld electronic apparatus such as mobile phone, notebook and calculator, and gradually expands to other fields
Exhibition.However there are serious security risk, the spontaneous combustions of battery of mobile phone, electric car electricity for traditional liquid electrolyte lithium ion battery
Phenomena such as pond is exploded causes attention of the people for cell safety, and the high electrolyte of research safety performance is present primary appoints
Business.
Solid polymer electrolyte is a kind of novel electrolyte, can have transmission as liquid state batteries electrolyte
The function of lithium ion, and its exposure in air will not combustion explosion；Meanwhile it is low self-discharging rate, good flexible
Property, it is environmental-friendly, can be used together with lithium anodes, higher energy density and excellent safety and stability etc. it is excellent
Point allows polymer dielectric to become the Main way of next-generation energy technology research and development.
Although solid polymer electrolyte has the above advantages, room-temperature conductivity is low, film formation time is long and higher
Interface resistance, limit the large-scale application of electrolyte.Therefore, it studies a kind of short and low with high conductivity, film formation time
The electrolyte of interface resistance is the main goal in research of current people.
The Chinese patent of Publication No. CN106916308A discloses a kind of lithium battery solid polymer electrolyte and Quan Gu
State lithium battery, the solid polymer are a kind of cross-linked polymers containing side-chain of polyelycol, can under room temperature and low temperature
Possess good cyclical stability, still, which contacts with anode poor, film formation time length, circulation volume
Conservation rate is low, and the extensive use of solid electrolyte needs to solve above-mentioned not foot point.
Summary of the invention
The purpose of the present invention is to provide a kind of solid polymer electrolyte and all-solid lithium-ion battery, including it is described solid
The all-solid lithium-ion battery of state polymer dielectric solves solid polymer electrolyte and contacts poor, solidification for electrolyte with anode
The problem that time is long and cyclic process capacity retention ratio is low, while there is good room-temperature conductivity and circulation volume.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of solid polymer electrolyte, including cross-linked polymer and lithium salts, the cross-linked polymers
Including with structural unit shown in formula I and formula II:
Wherein, R1For n-propyl, cyclohexyl, isobutyl group or phenyl；R2For urea propyl or aminopropyl；N=9~23, m=23
~46.
Preferably, the lithium salts is lithium perchlorate, lithium hexafluoro phosphate or bis trifluoromethyl sulfimide lithium.
Preferably, the preparation method of the cross-linked polymer, comprising the following steps:
Silane, polyethylene glycol and poly glycol monomethyl ether are mixed, cross-linking polymerization is carried out, obtains the cross-linked polymeric
Object；
The silane includes containing R1The silane of group and contain R2The silane of group.
Preferably, the molar ratio of the silane, polyethylene glycol and poly glycol monomethyl ether is 1:1:1.
Preferably, pH >=10 of the reaction system of the cross-linking polymerization.
Preferably, the temperature of the cross-linking polymerization is 85~95 DEG C, and the time of the cross-linking polymerization is 2~5
Hour.
Preferably, the molar ratio of the ether oxygen atom in the lithium ion in the lithium salts and the cross-linked polymer be 1:(8~
20)。
The present invention also provides a kind of all-solid lithium-ion batteries, including positive electrode, solid polymer electrolyte and negative electricity
Pole,
The positive electrode includes plus plate current-collecting body and positive electrode；
The positive electrode includes isocyanate crosslinking and positive active material；
The negative electrode includes negative current collector and negative electrode material；
The negative electrode material includes isocyanate crosslinking and negative electrode active material；
The solid polymer electrolyte is solid polymer electrolyte described in above-mentioned technical proposal.
Preferably, the solid polymer electrolyte is coated on the positive electrode or the negative electrode.
Preferably, the isocyanates in the isocyanate crosslinking in the positive electrode and the solid polymer electrolyte
The molar ratio of amino or urea groups is 1:(0.7~1.1 in matter)；
Or in the isocyanates in the isocyanate crosslinking in the negative electrode material and the solid polymer electrolyte
The molar ratio of amino or urea groups is 1:(0.7~1.1).
The present invention provides a kind of solid polymer electrolyte, including cross-linked polymer and lithium salts, the crosslinkable polymerics
Object includes with structural unit shown in formula I and formula II:
Wherein, R1For n-propyl, cyclohexyl, isobutyl group or phenyl；R2For urea propyl or aminopropyl；N=9~23, m=23
~46.The present invention also provides a kind of all-solid lithium-ion batteries, including electrode and solid polymer electrolyte；The electrode material
Material includes isocyanate crosslinking, electrode active material, binder and conductive agent；The solid polymer electrolyte is above-mentioned skill
The solid-state polymerization that solid polymer electrolyte described in art scheme or the preparation method as described in above-mentioned technical proposal are prepared
Object electrolyte.The present invention in conjunction with the solid polymer electrolyte, is formed using the isocyanate crosslinking in electrode material
Anode-solid polymer electrolyte continuous structure, eliminates the influence of interface resistance, improves lithium ion mobility efficiency.Institute
State isocyanate crosslinking in solid polymer electrolyte amino or urea groups be swift in response, can pass through control solid-state polymerization
The content of amino or urea groups adjusts mechanical strength and the curing time of final dielectric film in object electrolyte, obtained to have
The solid electrolyte of high mechanical strength can effectively prevent the formation of Li dendrite, it is ensured that stability in cyclic process and excellent
Capacity retention ratio.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of solid polymer electrolyte of the present invention.
Specific embodiment
In the present invention, if without specified otherwise, the component of all raw materials is commercially available production well known to those skilled in the art
Product.
The present invention provides a kind of solid polymer electrolyte, including cross-linked polymer and lithium salts, the cross-linked polymers
Including with structural unit shown in formula I and formula II:
Wherein, R1For n-propyl, cyclohexyl, isobutyl group or phenyl；R2For urea propyl or aminopropyl；N=9~23, m=23
~46.
In the present invention, the structure of the solid polymer electrolyte is as shown in Figure 1, the structure as shown in formula I and formula II
Unit carries out crosslinking bonding with disordered state.
In the present invention, the lithium salts is preferably lithium perchlorate, lithium hexafluoro phosphate or bis trifluoromethyl sulfimide lithium.
In the present invention, the preparation method of the cross-linked polymer preferably includes following steps:
Silane, polyethylene glycol and poly glycol monomethyl ether are mixed, cross-linking polymerization is carried out, obtains cross-linked polymer；
The silane includes containing R1The silane of group and contain R2The silane of group.
In the present invention, described to contain R1The silane of group is preferably n-propyl trimethoxy silane, cyclohexyl trimethoxy
Base silane, trimethoxysilane or phenyltrimethoxysila,e；It is described to contain R2The silane of group is preferably γ-ammonia third
Base trimethoxy silane or 3- urea propyl trimethoxy silicane.In the present invention, described to contain R1The silane of group and contain R2Base
The molar ratio of the silane of group is preferably (0.3~0.7): (0.3~0.7), more preferably (0.4~0.6): (0.4~0.6).
In the present invention, the polymerization degree n of the polyethylene glycol is preferably 9~23, correspondingly, the molecule of the polyethylene glycol
Amount preferably 400~1000；In the present invention, the polymerization degree n of the polyethylene glycol is preferably and the n in above-mentioned cross-linked polymer
It is worth identical.
In the present invention, the degree of polymerization m of the poly glycol monomethyl ether is preferably 23~46, correspondingly, the poly- second two
The molecular weight of alcohol monomethyl ether is preferably 1000~2000；In the present invention, the degree of polymerization m of the poly glycol monomethyl ether is preferably
It is identical as the m value in above-mentioned cross-linked polymer.
In the present invention, the molar ratio of the silane, polyethylene glycol and poly glycol monomethyl ether is preferably 1:1:1；This hair
Bright hybrid mode and sequence to the silane, polyethylene glycol and poly glycol monomethyl ether is used without any special restriction
Mode well known to those skilled in the art and sequence are mixed.
In the present invention, catalyst is further preferably added in the reaction system of the cross-linking polymerization；The catalyst is excellent
It is selected as tetrabutylammonium hydroxide；The tetrabutylammonium hydroxide and the molar ratio of polyethylene glycol are preferably (0.01~0.02): 1,
More preferably 0.012:1.In the present invention, the addition opportunity of the tetrabutylammonium hydroxide is preferably the silane, poly- second two
After the completion of the mixing of pure and mild poly glycol monomethyl ether, in mixture that the tetrabutylammonium hydroxide is added.
In the present invention, preferred pH >=10 of the reaction system of the cross-linking polymerization, more preferably 10.0~11.0, most
Preferably 10.4~10.8.The temperature of the cross-linking polymerization is preferably 85~95 DEG C, and more preferably 88~92 DEG C, most preferably
It is 90 DEG C；The time of the cross-linking polymerization is preferably 2~5 hours, and more preferably 3~4 hours.
After the completion of cross-linking polymerization, the present invention preferably obtains cross-linked polymer by way of vacuum distillation；The present invention
To the no any special restriction of vacuum distillation.
In the present invention, the molar ratio of the lithium ion in the lithium salts and the ether oxygen atom in the cross-linked polymer is preferred
For 1:(8~20), more preferably 1:(10~18), most preferably 1:(12~16).
In the present invention, the viscosity of the solid polymer electrolyte is preferably 3000~6500mpas, more preferably
3500~4500mpas, most preferably 3800~4200mpas.
In the present invention, the preparation method of the slurry containing solid polymer electrolyte described in above-mentioned technical proposal, it is excellent
Choosing the following steps are included:
Under conditions of anhydrous and oxygen-free, cross-linked polymer, lithium salts and acetone are mixed, obtained containing solid polymer electrolyte
The slurry of matter.
In the present invention, the preferred slurry of mixing carries out under stirring conditions, and the preferred slurry of mixing is first will
After cross-linked polymer and lithium salts mixing, then mix with acetone；The time of the cross-linked polymer and lithium salts mixing is preferably 1~
2h, the present invention to the dosage of the time mixed with acetone and acetone without any special restriction, using this field
The dosage of incorporation time and acetone known to technical staff, which can reach, reaches the viscosity of the solid polymer electrolyte
3000~6500mpas.The present invention to the rate of the stirring also without any special restriction, using field technology
Rate known to personnel simultaneously can reach above-mentioned purpose.
The present invention also provides a kind of all-solid lithium-ion batteries, including positive electrode, solid polymer electrolyte and negative electricity
Pole,
The positive electrode includes plus plate current-collecting body and positive electrode；
The positive electrode includes isocyanate crosslinking and positive active material；
The negative electrode includes negative current collector and negative electrode material；
The negative electrode material includes isocyanate crosslinking and negative electrode active material；
The solid polymer electrolyte is solid polymer electrolyte described in above-mentioned technical proposal.
In the present invention, the plus plate current-collecting body is preferably aluminium foil, and the negative current collector is preferably copper foil；The present invention couple
The aluminium foil or copper foil do not have any special restriction, using well known to those skilled in the art.
In the present invention, the positive electrode material includes isocyanate crosslinking and positive active material, is further preferably wrapped
Include binder and conductive agent；In the present invention, the isocyanate crosslinking be preferably hexamethylene diisocyanate trimer,
2,4- toluene diisocyanate trimers, 4,4'- diphenyl methane-diisocyanate trimer and isoflurane chalcone diisocyanate
One or more of tripolymer；When the isocyanate crosslinking be above-mentioned specific choice in it is two or more when, the present invention
The no any special restriction of proportion to the specific substance, is mixed by any proportion.The present invention to it is described just
Pole active material does not have any special restriction, using positive active material well known to those skilled in the art.In this hair
In bright, the positive active material can specifically be selected as cobalt acid lithium, LiFePO4 or nickel cobalt manganese 811
(LiNi0.8Co0.1Mn0.1O2)；The binder is preferably Kynoar；The conductive agent is preferably conductive black, acetylene
Black, Ketjen black or carbon nanotube.
In the present invention, the mass ratio of the positive active material, binder and conductive agent is preferably 7:1:2.It is described different
The molar ratio of amino or urea groups is preferably 1 in isocyanates and the solid polymer electrolyte in isocyanate cross-linking agent:
(0.7~1.0), more preferably 1:(0.9~1.0).
In the present invention, cathode pole electrode material includes that isocyanate crosslinking and negative electrode active material further preferably wrap
Include binder and conductive agent；In the present invention, the isocyanate crosslinking be preferably hexamethylene diisocyanate trimer,
2,4- toluene diisocyanate trimers, 4,4'- diphenyl methane-diisocyanate trimer and isoflurane chalcone diisocyanate
One or more of tripolymer；When the isocyanate crosslinking be above-mentioned specific choice in it is two or more when, the present invention
The no any special restriction of proportion to the specific substance, is mixed by any proportion.The present invention is to described negative
Pole active material does not have any special restriction, using negative electrode active material well known to those skilled in the art.In this hair
In bright, the negative electrode active material can specifically be selected as graphite or carbon nanotube；The binder is preferably carboxymethyl fibre
Tie up plain sodium；The conductive agent is preferably conductive black, acetylene black, Ketjen black or carbon nanotube.
In the present invention, the mass ratio of the negative electrode active material, binder and conductive agent is preferably 7:1:2.It is described different
The molar ratio of amino or urea groups is preferably 1 in isocyanates and the solid polymer electrolyte in isocyanate cross-linking agent:
(0.7~1.0), more preferably 1:(0.9~1.0).
In the present invention, it is also preferable to include positive battery shell, gasket and negative battery shells for the all-solid lithium-ion battery；
The present invention does not have any special restriction to the positive battery shell, gasket and negative battery shell, using those skilled in the art
It is well known.
The present invention also provides the preparation methods of the all-solid lithium-ion battery, preferably include following steps:
Slurry containing positive electrode is sprayed on plus plate current-collecting body surface, obtains anode；
Slurry containing negative electrode material is sprayed on negative current collector surface, obtains cathode；
The solid polymer electrolyte slurry is sprayed on the positive or negative pole, is obtaining being coated with electrolyte just
Pole or the cathode for being coated with electrolyte；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery.
Slurry containing positive electrode is sprayed on plus plate current-collecting body surface by the present invention, obtains anode；In the present invention, institute
It states the slurry containing positive electrode and preferably includes the positive electrode and organic solvent；The present invention does not appoint the organic solvent
What special restriction is guaranteed isocyanate-crosslinked described in solvent simultaneously using organic solvent well known to those skilled in the art
Agent；In the present invention, the organic solvent can be selected specifically to tetrahydrofuran；Use of the present invention to the organic solvent
No any special restriction is measured, using dosage well known to those skilled in the art and guarantees the slurry containing positive electrode
Viscosity in the range of 5000~7000mpas.In the present invention, the preparation of the slurry containing positive electrode
Process is preferably, and after positive electrode active materials, binder and conductive agent are mixed, sequentially adds isocyanate crosslinking and organic molten
Agent；The mixing preferably carries out under stirring conditions, and the time of the stirring is preferably 4~6h；The present invention is to the stirring
Rate there is no any special restriction, using rate well known to those skilled in the art.
In the present invention, the spraying preferably carries out under conditions of anhydrous and oxygen-free；The speed of the spraying is preferably 5~
10m/min, more preferably 6~8m/min；In the present invention, after the completion of the spraying, after preferably being carried out to the anode after spraying
Processing, the post-processing are preferably dried in vacuo, and the vacuum drying temperature is preferably 60~80 DEG C, more preferably 65~75
DEG C, most preferably 68~72 DEG C；The vacuum drying time is preferably 10min.
In the present invention, coating thickness of the active material in the positive electrode in anode is preferably 20~40 μm,
More preferably 30~40 μm.
Slurry containing negative electrode material is sprayed on negative current collector surface by the present invention, obtains cathode；In the present invention, institute
It states the slurry containing negative electrode material and preferably includes negative electrode material and organic solvent；The present invention does not have any spy to the organic solvent
Different restriction guarantees isocyanate crosslinking described in solvent i.e. simultaneously using organic solvent well known to those skilled in the art
It can；In the present invention, the organic solvent can be selected specifically to tetrahydrofuran；The present invention does not have the dosage of the organic solvent
There is any special restriction, using dosage well known to those skilled in the art and guarantees the viscous of the slurry containing negative electrode material
Degree is in the range of 5000~7000mpas.In the present invention, the preparation process of the slurry containing negative electrode material
Preferably, after negative electrode active material, binder and conductive agent being mixed, isocyanate crosslinking and organic solvent are sequentially added；
The mixing preferably carries out under stirring conditions, and the time of the stirring is preferably 4~6h；Speed of the present invention to the stirring
Rate does not have any special restriction, using rate well known to those skilled in the art.The mixing is preferably in the item of stirring
It is carried out under part, the time of the stirring is preferably 2~4h；The present invention does not have any special restriction to the rate of the stirring,
Using rate well known to those skilled in the art.
In the present invention, the spraying preferably carries out under conditions of anhydrous and oxygen-free；The speed of the spraying is preferably 5~
10m/min, more preferably 6~8m/min；In the present invention, after the completion of the spraying, after preferably being carried out to the cathode after spraying
Processing, the post-processing are preferably dried in vacuo, and the vacuum drying temperature is preferably 60~80 DEG C, more preferably 65~75
DEG C, most preferably 68~72 DEG C；The vacuum drying time is preferably 10min.
In the present invention, coating thickness of the active material in the negative electrode material in cathode is preferably 30~45 μm,
More preferably 35~40 μm.
Obtain it is described anode and cathode after, the present invention by the solid polymer electrolyte be sprayed on it is described anode and/or
On cathode, the anode for being coated with electrolyte and/or cathode are obtained；In the present invention, the thickness of the solid polymer electrolyte layer
Preferably 90~110 μm, more preferably 100 μm of degree.In the present invention, it is described spraying preferably under conditions of anhydrous and oxygen-free into
Row；The speed of the spraying is preferably 5~10m/min, more preferably 6~8m/min；In the present invention, the spraying is completed
Afterwards, the positive/negative after spraying is post-processed, is dried in vacuo 15 minutes at preferably 60~80 DEG C of the post-processing.
After obtaining the anode for being coated with electrolyte and/or cathode, the present invention is according to positive battery shell, anode, electrolyte, negative
The sequence of pole, gasket and negative battery shell is assembled, and all-solid lithium-ion battery is obtained；The present invention appoints described be assembled without
What special restriction, is carried out using process well known to those skilled in the art.
Solid polymer electrolyte provided by the invention and its all-solid lithium-ion battery are carried out below with reference to embodiment
Detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The ratio for being 1:1:0.5:0.5:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 1000)
10g, polyethylene glycol (molecular weight 400) 4g, γ-aminopropyltrimethoxysilane 0.90g and n-propyl trimethoxy silane
After 0.8g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:8, will
After 2h is mixed in 2.87gg bis trifluoromethyl sulfimide lithium and 4.08g solid polymer electrolyte, acetone is added, is glued
Degree is the solid polymer electrolyte slurry of 5000mpas；
7g LiFePO4,1g Kynoar and 2g acetylene black are mixed, after stirring 6h, 3.15g hexa-methylene two is added
Isocyanate trimer (the ratio between amino is 1:0.8 in the isocyanates and electrolyte wherein contained), continues to stir 1h, is added four
Hydrogen furans obtains the slurry containing positive electrode that viscosity is 5000mpas；Under conditions of anhydrous and oxygen-free, contain by described in
The slurry spraying (spray rate 10m/min) of positive electrode is on aluminium foil, and obtaining anode, (active material coating thickness is 30 μ
m)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, 3.15g hexa-methylene two is added
Isocyanate trimer (the ratio between amino is 1:0.8 in the isocyanates and electrolyte wherein contained), continues to stir 1h, is added four
Hydrogen furans obtains the slurry containing negative electrode material that viscosity is 7000mpas；Under conditions of anhydrous and oxygen-free, contain by described in
The slurry spraying (spray rate 10m/min) of negative electrode material is on copper foil, and obtaining cathode, (active material coating thickness is 40 μ
m)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 5000mpas is sprayed
(spray rate 10m/min) is crosslinked on anode, and at 70 DEG C with the hexamethylene diisocyanate trimer in anode
10min and solvent flashing, obtain solid polymer electrolyte layer (with a thickness of 100 μm, the hexamethylene diisocyanate trimerization
The molar ratio of amino is 1:0.8 in isocyanates and the solid polymer electrolyte in body)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, the charge and discharge of 0.5C are used
Carry out the test of cycle performance under multiplying power, the initial internal resistance of the all-solid lithium-ion battery is 400 Ω, and room temperature is discharged appearance for the first time
Amount is 117mAh/g, and after recycling 100 times, discharge capacity 108mAh/g, internal resistance is 530 Ω, capacity retention ratio 92.3%.
Embodiment 2
The ratio for being 1:1:0.6:0.4:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 1000)
10g, polyethylene glycol (molecular weight 1000) 10g, γ-aminopropyl trimethoxysilane 1.08g and cyclohexyl trimethoxy silane
After 0.816g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:10, will
After 2h is mixed in 1.06g lithium perchlorate and 4.94g solid polymer electrolyte, acetone is added, obtaining viscosity is 5000mpa
The solid polymer electrolyte slurry of s；
7g cobalt acid lithium, 1g Kynoar and 2g graphite are mixed, after stirring 6h.3.33g 4,4'- diphenylmethyl is added
Alkane-diisocyanate trimer (the ratio between amino is 1:0.9 in the isocyanates and electrolyte wherein contained), continues to stir 1h,
Tetrahydrofuran solvent is added, obtains the slurry containing positive electrode that viscosity is 5000mpas；Under conditions of anhydrous and oxygen-free,
By the slurry spraying (spray rate 7m/min) containing positive electrode on aluminium foil, anode (active material coating is obtained
With a thickness of 35 μm)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, 3.33g4,4'- diphenyl is added
Methane-diisocyanate trimer (the ratio between amino is 1:0.9 in the isocyanates and electrolyte wherein contained), continues to stir
Tetrahydrofuran is added in 1h, obtains the slurry containing negative electrode material that viscosity is 7000mpas；Under conditions of anhydrous and oxygen-free,
By the slurry spraying (spray rate 10m/min) containing negative electrode material on copper foil, cathode (active material coating is obtained
With a thickness of 35 μm)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 5000mpas is sprayed
(spray rate 10m/min) on anode, and at 70 DEG C with 4,4'- diphenyl methane-diisocyanate three in anode
Aggressiveness is crosslinked 10min and solvent flashing, obtain solid polymer electrolyte layer (with a thickness of 100 μm, 4, the 4'- diphenylmethyl
The molar ratio of amino is 1:0.9 in isocyanates and the solid polymer electrolyte in alkane-diisocyanate trimer)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, the charge and discharge of 0.5C are used
Carry out the test of cycle performance under multiplying power, the initial internal resistance of the all-solid lithium-ion battery is 500 Ω, and room temperature is discharged appearance for the first time
Amount is 90mAh/g, and after recycling 100 times, discharge capacity 84mAh/g, internal resistance is 590 Ω, capacity retention ratio 93.3%.
Embodiment 3
The ratio for being 1:1:0.7:0.3:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 2000)
20g, polyethylene glycol (molecular weight 1000) 10g, γ-aminopropyl trimethoxysilane 1.26g and trimethoxysilane
After 0.534g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:15, will
After 2h is mixed in 1.06g lithium perchlorate and 7.16g solid polymer electrolyte, acetone is added, obtaining viscosity is 6000mpa
The solid polymer electrolyte slurry of s；
7g LiFePO4,1g Kynoar and 2g acetylene black are mixed, after stirring 6h, 2.22g isophorone two is added
Isocyanate trimer (the ratio between amino is 1:0.9 in the isocyanates and electrolyte wherein contained), is added tetrahydrofuran solvent,
Obtain the slurry containing positive electrode that viscosity is 6000mpas；Under conditions of anhydrous and oxygen-free, described it will contain positive material
The slurry spraying (spray rate 7m/min) of material obtains anode on aluminium foil (active material coating thickness is 35 μm)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, 3.33g isophorone two is added
Isocyanate trimer (the ratio between amino is 1:0.9 in the isocyanates and electrolyte wherein contained), continues to stir 1h, is added four
Hydrogen furans obtains the slurry containing negative electrode material that viscosity is 7000mpas；Under conditions of anhydrous and oxygen-free, contain by described in
The slurry spraying (spray rate 10m/min) of negative electrode material is on copper foil, and obtaining cathode, (active material coating thickness is 40 μ
m)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 6000mpas is sprayed
(spray rate 10m/min) is crosslinked on anode, and at 70 DEG C with the isoflurane chalcone diisocyanate tripolymer in anode
10min and solvent flashing, obtain solid polymer electrolyte layer (with a thickness of 100 μm, the isoflurane chalcone diisocyanate trimerization
The molar ratio of amino is 1:0.9 in isocyanates and the solid polymer electrolyte in body)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, the charge and discharge of 0.5C are used
Carry out the test of cycle performance under multiplying power, the initial internal resistance of the all-solid lithium-ion battery is 530 Ω, and room temperature is discharged appearance for the first time
Amount is 85mAh/g, and after recycling 100 times, discharge capacity 77mAh/g, internal resistance is 600 Ω, capacity retention ratio 90.6%.
Embodiment 4
The ratio for being 1:1:0.7:0.3:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 1000)
10g, polyethylene glycol (molecular weight 2000) 20g, 3- urea propyl trimethoxy silicane 1.55g and phenyltrimethoxysila,e
After 0.59g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:10, will
After 2h is mixed in 1.52g lithium hexafluoro phosphate and 7.14g solid polymer electrolyte, acetone is added, obtaining viscosity is
The solid polymer electrolyte slurry of 6500mpas；
7g cobalt acid lithium, 1g Kynoar and 2g acetylene black are mixed, after stirring 6h.It is different that 2.22g hexa-methylene two is added
Cyanate tripolymer (the ratio between urea groups is 1:1 in the isocyanates and electrolyte wherein contained), additional amount tetrahydrofuran is glued
Degree is the slurry containing positive electrode of 6500mpas；Under conditions of anhydrous and oxygen-free, by the slurry containing positive electrode
Material spraying (spray rate 6m/min) obtains anode on aluminium foil (active material coating thickness is 30 μm)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, 2.22g hexa-methylene two is added
Isocyanate trimer (the ratio between urea groups is 1:1 in the isocyanates and electrolyte wherein contained), continues to stir 1h, tetrahydro is added
THF solvent obtains the slurry containing negative electrode material that viscosity is 7000mpas；Under conditions of anhydrous and oxygen-free, contain by described in
There is the slurry spraying (spray rate 10m/min) of negative electrode material on copper foil, obtaining cathode, (active material coating thickness is 40
μm)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 6500mpas is sprayed
(spray rate 10m/min) is crosslinked on anode, and at 70 DEG C with the hexamethylene diisocyanate trimer in anode
10min and solvent flashing, obtain solid polymer electrolyte layer (with a thickness of 100 μm, the hexamethylene diisocyanate trimerization
The molar ratio of amino is 1:1 in isocyanates and the solid polymer electrolyte in body)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；
By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, using under the charge-discharge magnification of 0.5C
The test of cycle performance is carried out, the initial internal resistance of the all-solid lithium-ion battery is 580 Ω, and discharge capacity is room temperature for the first time
89mAh/g, after recycling 100 times, discharge capacity 80mAh/g, internal resistance is 640 Ω, capacity retention ratio 89.9%.
Embodiment 5
The ratio for being 1:1:0.4:0.6:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 1000)
10g, polyethylene glycol (molecular weight 400) 4g, 3- urea propyl trimethoxy silicane 0.89g and trimethoxysilane
After 1.07g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:10, will
After 2h is mixed in 2.87g bis trifluoromethyl sulfimide lithium and 7.82g solid polymer electrolyte, acetone is added, is glued
Degree is the solid polymer electrolyte slurry of 6500mpas；
7g ternary material nickel cobalt manganese 811,1g Kynoar and 2g acetylene black are mixed, after stirring 6h, 1.78g six is added
Methylene diisocyanate tripolymer (the ratio between urea groups is 1:0.8 in the isocyanates and electrolyte wherein contained), is added tetrahydro
Furans obtains the slurry containing positive electrode that viscosity is 6500mpas；It, will be described containing just under conditions of anhydrous and oxygen-free
The slurry spraying (spray rate 8m/min) of pole material obtains anode on aluminium foil (active material coating thickness is 30 μm)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, 1.78g hexa-methylene two is added
Isocyanate trimer (the ratio between urea groups is 1:0.8 in the isocyanates and electrolyte wherein contained), continues to stir 1h, is added four
Hydrogen furans obtains the slurry containing negative electrode material that viscosity is 7000mpas；Under conditions of anhydrous and oxygen-free, contain by described in
The slurry spraying (spray rate 10m/min) of negative electrode material is on copper foil, and obtaining cathode, (active material coating thickness is 40 μ
m)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 6500mpas is sprayed
(spray rate 10m/min) is crosslinked on anode, and at 70 DEG C with the hexamethylene diisocyanate trimer in anode
10min and solvent flashing, obtain solid polymer electrolyte layer (with a thickness of 100 μm, the hexamethylene diisocyanate trimerization
The molar ratio of amino is 1:0.8 in isocyanates and the solid polymer electrolyte in body)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；
By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, using under the charge-discharge magnification of 0.5C
Carry out the test of cycle performance, the initial internal resistance of the all-solid lithium-ion battery are as follows: 430 Ω, discharge capacity is room temperature for the first time
160mAh/g, after recycling 100 times, discharge capacity 122mAh/g, internal resistance is 510 Ω, capacity retention ratio 76.3%.
Embodiment 6
The ratio for being 1:1:0.6:0.4:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 1500)
15g, polyethylene glycol (molecular weight 600) 6g, 3- urea propyl trimethoxy silicane 1.34g and n-propyl trimethoxy silane
After 0.66g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:13, will
After 2h is mixed in 2.87g bis trifluoromethyl sulfimide lithium and 6.49g solid polymer electrolyte, acetone is added, is glued
Degree is the solid polymer electrolyte slurry of 5500mpas；
7g LiFePO4,1g Kynoar and 2g acetylene black are mixed, after stirring 6h, 2.02g hexa-methylene two is added
Isocyanate trimer (the ratio between urea groups is 1:1 in the isocyanates and electrolyte wherein contained), is added tetrahydrofuran, is glued
Degree is the slurry containing positive electrode of 6500mpas；Under conditions of anhydrous and oxygen-free, by the slurry containing positive electrode
Material spraying (spray rate 7m/min) obtains anode on aluminium foil (active material coating thickness is 30 μm)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, 2.22g hexa-methylene two is added
Isocyanate trimer (the ratio between urea groups is 1:1 in the isocyanates and electrolyte wherein contained), continues to stir 1h, tetrahydro is added
Furans obtains the slurry containing negative electrode material that viscosity is 7000mpas；It, will be described containing negative under conditions of anhydrous and oxygen-free
The slurry spraying (spray rate 10m/min) of pole material obtains cathode on copper foil (active material coating thickness is 40 μm)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 5500mpas is sprayed
(spray rate 10m/min) is crosslinked on anode, and at 70 DEG C with the hexamethylene diisocyanate trimer in anode
10min and solvent flashing, obtain solid polymer electrolyte layer (with a thickness of 100 μm, the hexamethylene diisocyanate trimerization
The molar ratio of amino is 1:1 in isocyanates and the solid polymer electrolyte in body)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；
By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, using under the charge-discharge magnification of 0.5C
Carry out the test of cycle performance, the initial internal resistance of the all-solid lithium-ion battery are as follows: 470 Ω, discharge capacity is room temperature for the first time
112mAh/g, after recycling 100 times, discharge capacity 103mAh/g, internal resistance is 560 Ω, capacity retention ratio 92.0%.
Comparative example 1
The ratio for being 1:1:0.5:0.5:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 1000)
10g, polyethylene glycol (molecular weight 400) 4g, γ-aminopropyl trimethoxysilane 0.90g and n-propyl trimethoxy silane
After 0.80g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:13, will
After 2h is mixed in 2.87g bis trifluoromethyl sulfimide lithium and 4.08g solid polymer electrolyte, acetone is added, is glued
Degree is the solid polymer electrolyte slurry of 5000mpas；
7g LiFePO4,1g Kynoar and 2g acetylene black are mixed, after stirring 6h.Tetrahydrofuran is added, is glued
Degree is the slurry containing positive electrode of 5000mpas；Under conditions of anhydrous and oxygen-free, by the slurry containing positive electrode
Material spraying (spray rate 5m/min) obtains anode on aluminium foil (active material coating thickness is 30 μm)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, tetrahydrofuran is added, is glued
Degree is the slurry containing negative electrode material of 7000mpas；Under conditions of anhydrous and oxygen-free, by the slurry containing negative electrode material
Material spraying (spray rate 10m/min) obtains cathode on copper foil (active material coating thickness is 40 μm)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 5000mpas is sprayed
(spray rate 10m/min) keeps 10min solvent flashing on anode at 70 DEG C, obtains solid polymer electrolyte
Layer (with a thickness of 100 μm)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, the charge and discharge of 0.5C are used
Carry out the test of cycle performance under multiplying power, the initial internal resistance of the all-solid lithium-ion battery is 800 Ω, and room temperature is discharged appearance for the first time
Amount is 94mAh/g, and after recycling 100 times, discharge capacity 72mAh/g, internal resistance is 1100 Ω, capacity retention ratio 76.6%.
Comparative example 2
The ratio for being 1:1:0.6:0.4:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 1000)
10g, polyethylene glycol (molecular weight 1000) 10g, γ-aminopropyl trimethoxysilane 1.08g and n-propyl trimethoxy silane
After 0.64g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:10, will
After 2h is mixed in 1.06g lithium perchlorate and 5.30g solid polymer electrolyte, acetone is added, obtaining viscosity is 5000mpa
The solid polymer electrolyte slurry of s；
7g LiFePO4,1g Kynoar and 2g acetylene black are mixed, after stirring 6h, tetrahydrofuran is added, is glued
Degree is the slurry containing positive electrode of 6000mpas；Under conditions of anhydrous and oxygen-free, by the slurry containing positive electrode
Material spraying (spray rate 5m/min) obtains anode on aluminium foil (active material coating thickness is 30 μm)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, tetrahydrofuran is added.It is glued
Degree is the slurry containing negative electrode material of 7000mpas；Under conditions of anhydrous and oxygen-free, by the slurry containing negative electrode material
Material spraying (spray rate 10m/min) obtains cathode on copper foil (active material coating thickness is 40 μm)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 6000mpas is sprayed
(spray rate 10m/min) keeps 10min solvent flashing on anode at 70 DEG C, obtains solid polymer electrolyte
Layer (with a thickness of 100 μm)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, the charge and discharge of 0.5C are used
The test of cycle performance is carried out under multiplying power, the initial internal resistance of the all-solid lithium-ion battery is 1200 Ω, and room temperature is discharged for the first time
Capacity is 83mAh/g, and after circulation 100 times, discharge capacity 65mAh/g, internal resistance is 1400 Ω, capacity retention ratio 78.3%.
Comparative example 3
The ratio for being 1:1:0.7:0.3:0.012 according to molar ratio, by poly glycol monomethyl ether (molecular weight 2000)
20g, polyethylene glycol (molecular weight 1000) 10g, γ-aminopropyl trimethoxysilane 1.26g and n-propyl trimethoxy silane
After 0.49g mixing, 0.03g tetrabutylammonium hydroxide is added, regulation system pH > 10, after heating 5 hours at 90 DEG C, decompression is steamed
It evaporates, obtains solid polymer electrolyte；
The ratio that molar ratio according to ether oxygen atom in lithium ion and the solid polymer electrolyte is 1:10, will
After 2h is mixed in 1.52g lithium hexafluoro phosphate and 7.16g solid polymer electrolyte, acetone is added, obtaining viscosity is
The solid polymer electrolyte slurry of 6000mpas；
7g LiFePO4,1g Kynoar and 2g acetylene black are mixed, after stirring 6h, tetrahydrofuran is added, is glued
Degree is the slurry containing positive electrode of 6000mpas；Under conditions of anhydrous and oxygen-free, by the slurry containing positive electrode
Material spraying (spray rate 5m/min) obtains anode on aluminium foil (active material coating thickness is 35 μm)；
7g graphite, 1g sodium carboxymethylcellulose and 2g acetylene black are mixed, after stirring 4h, tetrahydrofuran is added, is glued
Degree is the slurry containing negative electrode material of 7000mpas；Under conditions of anhydrous and oxygen-free, by the slurry containing negative electrode material
Material spraying (spray rate 10m/min) obtains cathode on copper foil (active material coating thickness is 40 μm)；
In the environment of anhydrous and oxygen-free, the solid polymer electrolyte slurry that the viscosity is 6000mpas is sprayed
(spray rate 10m/min) keeps 10min solvent flashing on anode at 70 DEG C, obtains solid polymer electrolyte
Layer (with a thickness of 100 μm)；
It is assembled, is obtained complete according to the sequence of positive battery shell, anode, electrolyte, cathode, gasket and negative battery shell
Solid lithium ion battery；By the all-solid lithium-ion battery in the voltage range of 1.5~3.9V, the charge and discharge of 0.5C are used
The test of cycle performance is carried out under multiplying power, the initial internal resistance of the all-solid lithium-ion battery is 1100 Ω, and room temperature is discharged for the first time
Capacity is 86mAh/g, and after circulation 100 times, discharge capacity 70mAh/g, internal resistance is 1300 Ω, capacity retention ratio 81.4%.
As seen from the above embodiment, the present invention provide all-solid lithium-ion battery have at room temperature preferable conductivity and
Preferable stable circulation performance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of solid polymer electrolyte, including cross-linked polymer and lithium salts, which is characterized in that the cross-linked polymer includes
With structural unit shown in formula I and formula II:
Wherein, R1For n-propyl, cyclohexyl, isobutyl group or phenyl；R2For urea propyl or aminopropyl；N=9~23, m=23~46.
2. solid polymer electrolyte as described in claim 1, which is characterized in that the lithium salts is lithium perchlorate, hexafluoro phosphorus
Sour lithium or bis trifluoromethyl sulfimide lithium.
3. solid polymer electrolyte as described in claim 1, which is characterized in that the preparation method of the cross-linked polymer,
The following steps are included:
Silane, polyethylene glycol and poly glycol monomethyl ether are mixed, cross-linking polymerization is carried out, obtains the cross-linked polymer；
The silane includes containing R1The silane of group and contain R2The silane of group.
4. solid polymer electrolyte as claimed in claim 3, which is characterized in that the silane, polyethylene glycol and poly- second two
The molar ratio of alcohol monomethyl ether is 1:1:1.
5. solid polymer electrolyte as claimed in claim 3, which is characterized in that the reaction system of the cross-linking polymerization
PH >=10.
6. solid polymer electrolyte as claimed in claim 3 or 5, which is characterized in that the temperature of the cross-linking polymerization
It is 85~95 DEG C, the time of the cross-linking polymerization is 2~5 hours.
7. solid polymer electrolyte as described in claim 1, which is characterized in that lithium ion and the friendship in the lithium salts
The molar ratio of ether oxygen atom in linked polymer is 1:(8~20).
8. a kind of all-solid lithium-ion battery, including positive electrode, solid polymer electrolyte and negative electrode, which is characterized in that
The positive electrode includes plus plate current-collecting body and positive electrode；
The positive electrode includes isocyanate crosslinking and positive active material；
The negative electrode includes negative current collector and negative electrode material；
The negative electrode material includes isocyanate crosslinking and negative electrode active material；
The solid polymer electrolyte is the described in any item solid polymer electrolytes of claim 1~7.
9. all-solid lithium-ion battery as claimed in claim 8, which is characterized in that the solid polymer electrolyte is coated in
On the positive electrode or the negative electrode.
10. all-solid lithium-ion battery as claimed in claim 8, which is characterized in that the isocyanates in the positive electrode
The molar ratio of amino or urea groups is 1:(0.7~1.1 in isocyanates and the solid polymer electrolyte in crosslinking agent)；
Or amino in the isocyanates in the isocyanate crosslinking in the negative electrode material and the solid polymer electrolyte
Or the molar ratio of urea groups is 1:(0.7~1.1).
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