CN106960982B - A kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries - Google Patents
A kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery successively includes positive lamella, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, cathode lamella from top to bottom.Electrolyte conductivity with higher can be greater than 10 at room temperature‑4S/cm, and elasticity modulus is greater than 0.1GPa；The multilayer electrolyte structure has high elastic modulus and low elastic modulus electrolyte simultaneously, high elastic modulus electrolyte can stop Li dendrite, and low elastic modulus electrolyte is able to maintain solid electrolyte and comes into full contact with battery plus-negative plate, reduce interface impedance, the increase for inhibiting the internal resistance of cell in cyclic process, improves the cycle life and specific capacity of battery.Meanwhile the battery applications lithium an- ode improves the specific capacity of battery；By multilayer electrolyte structure, fabulous contact can be obtained by enabling between electrode and electrolyte, improve the charging and discharging capabilities of battery.
Description
Technical field
The invention belongs to lithium battery preparation fields, and in particular to a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries.
Background technique
Now with the development of mobile device, electric vehicle it is universal, also increasingly to battery energy storage cruising ability demand
It is high.The lithium ion battery of excellent combination property is as mobile device and the major impetus source of electric vehicle, the lithium battery body at present
Owner will be by containing lithium metal oxide anode, membrane for polymer, carbonic ester or ethers electrolyte, graphite or graphite dopping silicon materials
Cathode is constituted.And anode uses lithium metal oxide, cathode uses the system of graphite already close to the reason of quality of materials specific energy
By the limit, about 250 to 300Wh/kg.And the cathode of doped silicon, since silicon is during charging and discharging lithium battery, volume can occur
Great variety causes battery cathode powdered capacity attenuation even to cause explosion.
Replacement electrode material, especially cathode is changed to lithium metal simple substance (tool by the graphite material of graphite or doped silicon
Have 3800mAh/g capacity, standard electrode EMF -3.04V) or lithium alloy can greatly promote the specific capacity of lithium ion battery.
However, lithium branch can inevitably be generated by directly carrying out charge and discharge using cathode in traditional electrolyte diaphragm serondary lithium battery
Crystalline substance, to bring the rapid decaying and the risk of internal short-circuit of capacity.Thus application has consolidating for certain rigidity (high elastic modulus)
State electrolyte can effectively hinder the generation of Li dendrite and avoid the risk of internal short-circuit.
But the elasticity modulus high due to this solid electrolyte, higher interface resistance is generated between meeting and positive and negative anodes
It is anti-, the transfer ability of lithium ion is reduced, the internal resistance of cell is increased, reduces the capacity under battery high magnification.And with circulating battery,
The volume of positive and negative anodes changes, and positive and negative anodes are detached from electrolyte, can further increase the internal resistance of battery.
Summary of the invention
For the present invention in view of the above-mentioned problems, compound by multilayer electrolyte, reduction interface impedance keeps charge and discharge cycles process
The continuous contact of middle positive and negative anodes and electrolyte keeps the internal resistance of battery not to be widely varied, so that height ratio capacity is obtained,
The performances such as safety and the cycle life of battery are kept simultaneously.
It realizes the technical scheme is that a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery
It from top to bottom successively include positive lamella, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electricity
Solve matter layer II, cathode lamella；Specific step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) positive electrode active materials are coated on aluminium foil, form the positive lamella of battery；
(3) lithium salts is dissolved in organic solvent or is uniformly mixed lithium salts with epoxy resin to obtain low elastic modulus electricity
Xie Zhi；
(4) high molecular polymer is mixed with lithium salts, is heated to 300-350 DEG C of holding 0.5-12h, it will after being cooled to room temperature
Mixture is broken into particle, and particle is extruded into roll film at being 300-350 DEG C in temperature using extruder, is cooled to room
Temperature；Electron acceptor is dissolved in dioxane and obtains maceration extract, obtained roll film is put into maceration extract later, in 60-
Airtight heating 1-30h at 200 DEG C, obtains high elastic modulus electrolyte layer；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 0.5-12h at 60-80 DEG C, obtain lithium battery.
Positive electrode active materials in the step (2) are nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4, titanium
Sour lithium, phosphorus, sulphur, more lithium sulfides or LiFePO4.
Lithium salts is LiOH, LiTFSI, LiFSI, LiFNFSI or LiClO in the step (3) and step (4)4。
Organic solvent in the step (3) is propene carbonate, ethylene carbonate, diethyl carbonate or dimethyl carbonate
In it is any two kinds combination.
High molecular polymer is polyphenylene sulfide or polyphenylene oxide in the step (4), and electron acceptor is tetrachloroquinone, dichloro two
Benzonitrile quinone, tetracyanoethylene, four cyano are to secondary methylbenzoquinone or oxygen molecule.
The mass ratio of high molecular polymer, lithium salts and electron acceptor is 10:(2-8 in the step (4)): (1-10).
It is liquid electrolyte that lithium salts is dissolved in low elastic modulus electrolyte obtained in organic solvent by the step (3),
The concentration of lithium salts is 0.5-1.5mol/L；Acrylate, fluoropolymer or epoxy resin are added into liquid electrolyte to obtain
Gel electrolyte, the quality that acrylate, fluoropolymer or epoxy resin is added is the 1-30% of liquid electrolyte quality.
Lithium salts and epoxy resin in the step (3) are 1:(4-20 according to the molar ratio of lithium ion and oxygen atom), it will
Lithium salts is uniformly mixed to obtain low elastic modulus electrolyte with epoxy resin.
The beneficial effects of the present invention are: the present invention is prepared for the lithium ion battery with multilayer electrolyte structure, the electrolysis
Matter conductivity with higher can be greater than 10 at room temperature-4S/cm, and elasticity modulus is greater than 0.1GPa；The multilayer electrolyte
Structure has high elastic modulus and low elastic modulus electrolyte simultaneously, and high elastic modulus electrolyte can stop Li dendrite, and low
Elasticity modulus electrolyte is able to maintain solid electrolyte and comes into full contact with battery plus-negative plate, interface impedance is reduced, in cyclic process
The middle increase for inhibiting the internal resistance of cell, improves the cycle life and specific capacity of battery.Meanwhile the battery applications lithium an- ode improves
The specific capacity of battery；It is likely to fit closely between solid electrolyte and electrode and causes interface impedance, increase the interior of battery
Resistance, reduces the capacity of battery, by multilayer electrolyte structure, fabulous contact can be obtained by enabling between electrode and electrolyte, be mentioned
The charging and discharging capabilities of high battery.Meanwhile as the circulation of battery, the volume of electrode can also change, lead to electrode and solid-state
The separation of electrolyte causes capacity decline, and using multilayer electrolyte, the small electrolyte of elasticity modulus can become with electrode volume
Change and change, remains the close contact of electrode and electrolyte.Thus the lithium battery of forecast scheme configuration has specific capacity height, safety
Good, the good feature of cycle life of property.
Detailed description of the invention
Fig. 1 is lithium battery different multiplying discharge capacity curve in embodiment 1.
Fig. 2 is lithium battery cycle life schematic diagram in embodiment 1.
Specific embodiment
Embodiment 1
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) LiMn2O4 is coated on aluminium foil, forms the positive lamella of battery；
(3) by LiPF6It is dissolved in the in the mixed solvent of propene carbonate and ethylene carbonate, is uniformly mixed and obtains low elasticity
Modulus electrolyte (liquid electrolyte), LiPF6Concentration be 1mol/L；
(4) polyphenylene sulfide is mixed with LiTFSI, is heated to 300 DEG C of holding 12h, smashes mixture after being cooled to room temperature
At particle, particle is extruded into roll film at being 300 DEG C in temperature using extruder, is cooled to room temperature；Tetrachloroquinone is molten
Maceration extract is obtained in dioxane, and obtained roll film is put into maceration extract later, the airtight heating 30h at 60 DEG C,
Obtain high elastic modulus electrolyte layer；The mass ratio of polyphenylene sulfide, LiTFSI and tetrachloroquinone is 10:2:1；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 12h at 60 DEG C, obtain lithium battery.
Battery can keep extraordinary capacity under room temperature high magnification as can be seen from Figure 1, have and liquid electrolyte
The approximate high rate capability of lithium battery, the lithium battery using single layer solid electrolyte significantly larger than reported at present is in room temperature high power
Discharge capacity under rate.
Fig. 2 can be seen that in the case where application lithium an- ode, the cycle life of MULTILAYER COMPOSITE solid electrolyte than
Common diaphragm liquid electrolyte lithium battery is long very much, and the safety problems such as internal short-circuit does not occur after several hundred circulations.Body
The advantage of the multilayer solid electrolytic matter on lithium metal battery is revealed.
Embodiment 2
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) LiMn2O4 is coated on aluminium foil, forms the positive lamella of battery；
(3) LiTFSI is dissolved in the in the mixed solvent of propene carbonate and diethyl carbonate, is uniformly mixed and obtains low bullet
Property modulus electrolyte (liquid electrolyte), the concentration of LiTFSI is 0.7mol/L；
(4) polyphenylene oxide is mixed with LiTFSI, is heated to 310 DEG C of holding 10h, is broken into mixture after being cooled to room temperature
Particle is extruded into roll film at being 310 DEG C in temperature using extruder, is cooled to room temperature by particle；By dichlorodicyanobenzoquinone
It is dissolved in dioxane and obtains maceration extract, obtained roll film is put into maceration extract later, the airtight heating at 80 DEG C
25h obtains high elastic modulus electrolyte layer；The mass ratio of polyphenylene oxide, LiTFSI and dichlorodicyanobenzoquinone is 10:3:2；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 10h at 65 DEG C, obtain lithium battery.
Embodiment 3
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) lithium titanate is coated on aluminium foil, forms the positive lamella of battery；
(3) LiFSI is dissolved in the in the mixed solvent of ethylene carbonate and dimethyl carbonate, is uniformly mixed and obtains low elasticity
Modulus electrolyte (liquid electrolyte), the concentration of LiFSI are 1.0mol/L；
(4) polyphenylene sulfide is mixed with LiFSI, is heated to 320 DEG C of holding 8h, is broken into mixture after being cooled to room temperature
Particle is extruded into roll film at being 320 DEG C in temperature using extruder, is cooled to room temperature by particle；Tetracyanoethylene is dissolved in
Maceration extract is obtained in dioxane solvent, and obtained roll film is put into maceration extract later, the airtight heating at 120 DEG C
22h obtains high elastic modulus electrolyte；The mass ratio of polyphenylene sulfide, LiFSI and tetracyanoethylene is 10:4:4；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 8h at 70 DEG C, obtain lithium battery.
Embodiment 4
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) phosphorus is coated on aluminium foil, forms the positive lamella of battery；
(3) LiFNFSI is dissolved in the in the mixed solvent of diethyl carbonate and dimethyl carbonate, is uniformly mixed liquid electrolyte
Matter, the concentration of LiFNFSI are 1.2mol/L, epoxy resin (bisphenol A type epoxy resin) are added into liquid electrolyte, asphalt mixtures modified by epoxy resin
The additional amount of rouge is the 15% of liquid electrolyte quality, obtains low elastic modulus electrolyte；
(4) polyphenylene oxide is mixed with LiFNFSI, is heated to 330 DEG C of holding 6h, is broken into mixture after being cooled to room temperature
Particle is extruded into roll film at being 330 DEG C in temperature using extruder, is cooled to room temperature by particle；By four cyano to secondary
Methylbenzoquinone, which is dissolved in dioxane, obtains maceration extract, and obtained roll film is put into maceration extract later, close at 150 DEG C
Heating 15h is closed, high elastic modulus electrolyte layer is obtained；The mass ratio of polyphenylene oxide, LiFNFSI and four cyano to secondary methylbenzoquinone
It is 10:5:5；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 5h at 75 DEG C, obtain lithium battery.
Embodiment 5
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) more lithium sulfides are coated on aluminium foil, form the positive lamella of battery；
(3) by LiClO4It is dissolved in the in the mixed solvent of propene carbonate and dimethyl carbonate, LiClO4Concentration be
0.7mol/L obtains liquid electrolyte, and acrylate (ethoxyquin pentaerythritol tetraacrylate) is added into liquid electrolyte,
It is uniformly mixed and obtains low elastic modulus electrolyte (gel electrolyte), acrylate (ethoxyquin pentaerythritol tetraacrylate)
Additional amount is the 1% of liquid electrolyte quality；
(4) polyphenylene sulfide is mixed with LiOH, is heated to 340 DEG C of holding 4h, is broken into mixture after being cooled to room temperature
Particle is extruded into roll film at being 340 DEG C in temperature using extruder, is cooled to room temperature by particle；Oxygen molecule is dissolved in two
Maceration extract is obtained in six ring solvent of oxygen, obtained roll film is put into maceration extract later, the airtight heating 10h at 170 DEG C,
Obtain high elastic modulus electrolyte layer；The mass ratio of polyphenylene sulfide, LiOH and oxygen molecule is 10:6:7；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 0.5h at 80 DEG C, obtain lithium battery.
Embodiment 6
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) LiFePO4 is coated on aluminium foil, forms the positive lamella of battery；
(3) by LiClO4It is dissolved in the in the mixed solvent of propene carbonate and diethyl carbonate, LiClO4Concentration be
1.5mol/L obtains liquid electrolyte, and fluoropolymer is added into liquid electrolyte, is uniformly mixed and obtains low elastic modulus electricity
It solves matter (gel electrolyte), fluoropolymer-containing additional amount is the 30% of liquid electrolyte quality；
(4) polyphenylene oxide is mixed with LiOH, is heated to 350 DEG C of holding 0.5h, is broken into mixture after being cooled to room temperature
Particle is extruded into roll film at being 350 DEG C in temperature using extruder, is cooled to room temperature by particle；Tetracyanoethylene is dissolved in
Maceration extract is obtained in dioxane solvent, and obtained roll film is put into maceration extract later, the airtight heating at 150 DEG C
15h obtains high elastic modulus electrolyte；The mass ratio of polyphenylene oxide, LiOH and tetracyanoethylene is 10:8:10；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 12h at 70 DEG C, obtain lithium battery.
Embodiment 7
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) nickel-cobalt-manganese ternary material (NCM622) is coated on aluminium foil, forms the positive lamella of battery；
(3) by LiClO4It is uniformly mixed with epoxy resin and obtains low elastic modulus electrolyte, the lithium ion and ring in lithium salts
The molar ratio of oxygen atom in oxygen resin is 1:4；
(4) polyphenylene sulfide is mixed with LiOH, is heated to 320 DEG C of holding 8h, is broken into mixture after being cooled to room temperature
Particle is extruded into roll film at being 300 DEG C in temperature using extruder, is cooled to room temperature by particle；Tetrachloroquinone is dissolved in
Maceration extract is obtained in dioxane, obtained roll film is put into maceration extract later, and airtight heating 15h, obtains at 150 DEG C
To high elastic modulus electrolyte layer；The mass ratio of polyphenylene sulfide, LiOH and tetrachloroquinone is 10:7:5；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 8h at 70 DEG C, obtain lithium battery.
Embodiment 8
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) nickel cobalt aluminium ternary material (NCA) is coated on aluminium foil, forms the positive lamella of battery；
(3) by LiClO4It is uniformly mixed with epoxy resin (polyethyleneglycol diglycidylether) and obtains low elastic modulus electrolysis
Matter, the molar ratio of the oxygen atom in lithium ion and epoxy resin in lithium salts are 1:10；
(4) polyphenylene oxide is mixed with LiOH, is heated to 320 DEG C of holding 10h, be broken into mixture after being cooled to room temperature
Particle is extruded into roll film at being 330 DEG C in temperature using extruder, is cooled to room temperature by grain；Dichlorodicyanobenzoquinone is molten
Maceration extract is obtained in dioxane solvent, and obtained roll film is put into maceration extract later, the airtight heating at 180 DEG C
20h obtains high elastic modulus electrolyte layer；The mass ratio of polyphenylene oxide, LiOH and dichlorodicyanobenzoquinone is 10:3:8；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 10h at 75 DEG C, obtain lithium battery.
Embodiment 9
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery from top to bottom according to
It is secondary include positive lamella, it is low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative
Pole piece layer；Preparation step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) nickel cobalt aluminium ternary material (NCA) is coated on aluminium foil, forms the positive lamella of battery；
(3) LiTFSI and epoxy resin (polypropylene glycol diglycidyl ether) are uniformly mixed and obtain low elastic modulus electrolysis
Matter, the molar ratio of the oxygen atom in lithium ion and epoxy resin in lithium salts are 1:20；
(4) polyphenylene oxide is mixed with LiTFSI, is heated to 320 DEG C of holding 10h, is broken into mixture after being cooled to room temperature
Particle is extruded into roll film at being 330 DEG C in temperature using extruder, is cooled to room temperature by particle；By dichlorodicyanobenzoquinone
It is dissolved in dioxane solvent and obtains maceration extract, obtained roll film is put into maceration extract later, it is closed at 180 DEG C to add
Hot 20h obtains high elastic modulus electrolyte layer；The mass ratio of polyphenylene oxide, LiTFSI and dichlorodicyanobenzoquinone is 10:3:8；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high resiliency that step (4) obtains
Modulus electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between injection step (3) obtain
Low elastic modulus electrolyte forms low elastic modulus electrolyte layer II, between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that injection step (3) obtains forms low elastic modulus electrolyte layer I, after stacking from top to bottom successively
Be positive pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer, seals after stacking, heats 10h at 75 DEG C, obtain lithium battery.
Claims (8)
1. a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, it is characterised in that: the lithium battery successively wraps from top to bottom
Include positive lamella, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, negative electrode tab
Layer；Specific step is as follows:
(1) lithium metal is fitted on copper foil by way of plating or roll-in, forms the cathode lamella of battery；
(2) positive electrode active materials are coated on aluminium foil, form the positive lamella of battery；
(3) lithium salts is dissolved in organic solvent or is uniformly mixed lithium salts with epoxy resin to obtain low elastic modulus electrolyte；
(4) high molecular polymer is mixed with lithium salts, is heated to 300-350 DEG C of holding 0.5-12h, it will mixing after being cooled to room temperature
Object is broken into particle, and particle is extruded into roll film at being 300-350 DEG C in temperature using extruder, is cooled to room temperature；It will
Electron acceptor, which is dissolved in dioxane, obtains maceration extract, obtained roll film is put into maceration extract later, at 60-200 DEG C
Lower airtight heating 1-30h, obtains high elastic modulus electrolyte layer；
(5) by the positive lamella that cathode lamella that step (1) obtains, step (2) obtain and the high elastic modulus that step (4) obtains
Electrolyte layer is laminated, backward negative electrode tab layer and high elastic modulus electrolyte layer between the obtained low bullet of injection step (3)
Property modulus electrolyte, form low elastic modulus electrolyte layer II, injected between positive lamella and high elastic modulus electrolyte layer
Low elastic modulus electrolyte that step (3) obtains forms low elastic modulus electrolyte layer I, is successively positive from top to bottom after stacking
Pole piece layer, low elastic modulus electrolyte layer I, high elastic modulus electrolyte layer, low elastic modulus electrolyte layer II, cathode lamella,
It is sealed after stacking, heats 0.5-12h at 60-80 DEG C, obtain lithium battery.
2. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that: the step
(2) positive electrode active materials in are nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4, lithium titanate, phosphorus, sulphur, more vulcanizations
Lithium or LiFePO4.
3. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that: the step
(3) and in step (4) lithium salts is LiOH, LiTFSI, LiFSI, LiFNFSI, LiClO4Or LiPF6。
4. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that: the step
(3) organic solvent in is any two kinds of groups in propene carbonate, ethylene carbonate, diethyl carbonate or dimethyl carbonate
It closes.
5. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that: the step
(4) in high molecular polymer be polyphenylene sulfide or polyphenylene oxide, electron acceptor be tetrachloroquinone, dichlorodicyanobenzoquinone, tetracyanoethylene,
Four cyano is to secondary methylbenzoquinone or oxygen molecule.
6. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that: the step
(4) mass ratio of high molecular polymer, lithium salts and electron acceptor is 10:(2-8 in): (1-10).
7. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that: the step
(3) lithium salts is dissolved in low elastic modulus electrolyte obtained in organic solvent is liquid electrolyte, and the concentration of lithium salts is 0.5-
1.5mol/L；Acrylate, fluoropolymer or epoxy resin are added into liquid electrolyte and obtains gel electrolyte, is added third
The quality of olefin(e) acid ester, fluoropolymer or epoxy resin is the 1-30% of liquid electrolyte quality.
8. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that: the step
(3) lithium salts and epoxy resin in are 1:(4-20 according to the molar ratio of lithium ion and oxygen atom), lithium salts and epoxy resin are mixed
It closes and uniformly obtains low elastic modulus electrolyte.
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