CN106960982A - 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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- CN106960982A CN106960982A CN201710388187.0A CN201710388187A CN106960982A CN 106960982 A CN106960982 A CN 106960982A CN 201710388187 A CN201710388187 A CN 201710388187A CN 106960982 A CN106960982 A CN 106960982A
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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
- H01M10/058—Construction or manufacture
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention provides a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery includes positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella successively from top to bottom.The electrolyte has higher electrical conductivity, and 10 can be more than at room temperature‑4S/cm, and elastic modelling quantity is more 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 can keep solid electrolyte fully to be contacted with battery plus-negative plate, reduce interface impedance, suppress the increase of the internal resistance of cell in cyclic process, improve 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, make and fabulous contact is resulted between electrode and electrolyte, improve the charging and discharging capabilities of battery.
Description
Technical field
The invention belongs to lithium battery preparation field, and in particular to a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries.
Background technology
Now with the development of mobile device, the popularization of electric vehicle, to battery energy storage endurance demand also increasingly
It is high.The lithium ion battery of current excellent combination property is originated as mobile device and the major impetus of electric motor car, the lithium battery body
Owner will be by positive pole containing lithium metal oxide, membrane for polymer, carbonic ester or ethers electrolyte, graphite or graphite dopping silicon materials
Negative pole is constituted.And positive pole uses lithium metal oxide, negative pole 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 negative pole of doped silicon, because silicon is during charging and discharging lithium battery, volume can occur
Great variety, causes GND powdered capacity attenuation or even triggers blast.
Change electrode material, particularly negative pole and lithium metal simple substance is replaced by by the graphite material of graphite or doped silicon（Tool
There are 3800mAh/g capacity, standard electrode EMF -3.04V）Or lithium alloy can greatly lift the specific capacity of lithium ion battery.
However, in traditional electrolyte barrier film serondary lithium battery, lithium branch can inevitably be generated by directly applying negative pole to carry out discharge and recharge
Crystalline substance, so as to bring rapid decay and the risk of internal short-circuit of capacity.Thus application has certain rigidity（High elastic modulus）Consolidate
State electrolyte can effectively hinder the generation of Li dendrite and avoid the risk of internal short-circuit.
But, due to the high elastic modelling quantity of this solid electrolyte, higher interface resistance is produced between meeting and both positive and negative polarity
It is anti-, the transfer ability of lithium ion is reduced, increases the capacity under the internal resistance of cell, reduction battery high magnification.And with circulating battery,
The volume of both positive and negative polarity changes, and both positive and negative polarity departs from electrolyte, can further increase the internal resistance of battery.
The content of the invention
The present invention is regarding to the issue above, compound by multilayer electrolyte, reduces interface impedance, keeps charge and discharge cycles process
The continuous contact of middle both positive and negative polarity and electrolyte, keeping the internal resistance of battery will not be widely varied, so that height ratio capacity is obtained,
The performances such as the security and cycle life of battery are kept simultaneously.
Realize the technical scheme is that：A kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, the lithium battery
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus electricity successively from top to bottom
Solve matter layer II, negative pole lamella；Comprise the following steps that：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）Positive electrode active materials are coated on aluminium foil, the positive pole lamella of battery is formed；
（3）Lithium salts is dissolved in organic solvent or is well mixed lithium salts with epoxy resin and obtains low elastic modulus electrolyte；
（4）High molecular polymer is mixed with lithium salts, 300-350 DEG C of holding 0.5-12h is heated to, being cooled to after room temperature will mixing
Thing is broken into particle, and particle is extruded into roll film in the case where temperature is 300-350 DEG C using extruder, room temperature is cooled to；Will
Electron acceptor, which is dissolved in dioxane, obtains maceration extract, obtained roll film is put into maceration extract afterwards, at 60-200 DEG C
Lower airtight heating 1-30h, obtains high elastic modulus dielectric substrate；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 0.5-12h at 60-80 DEG C, is obtained lithium battery.
The step（2）In positive electrode active materials be nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4, titanium
Sour lithium, phosphorus, sulphur, many lithium sulfides or LiFePO4.
The step（3）And step（4）Middle lithium salts is LiOH, LiTFSI, LiFSI, LiFNFSI or LiClO4。
The step（3）In organic solvent be propene carbonate, ethylene carbonate, diethyl carbonate or dimethyl carbonate
In it is any two kinds combination.
The step（4）Middle high molecular polymer is polyphenylene sulfide or polyphenylene oxide, and electron acceptor is tetrachloroquinone, dichloro two
Benzonitrile quinone, tetracyanoethylene, four cyano are to secondary methylbenzoquinone or oxygen molecule.
The step（4）The mass ratio of middle high molecular polymer, lithium salts and electron acceptor is 10：（2-8）：（1-10）.
The step（3）It is liquid electrolyte that lithium salts is dissolved in the low elastic modulus electrolyte obtained in organic solvent,
The concentration of lithium salts is 0.5-1.5mol/L；Acrylate, fluoropolymer or epoxy resin is added into liquid electrolyte to obtain
Gel electrolyte, the quality for adding acrylate, fluoropolymer or epoxy resin is the 1-30% of liquid electrolyte quality.
The step（3）In lithium salts and epoxy resin according to lithium ion and oxygen atom mol ratio be 1：（4-20）, will
Lithium salts is well mixed with epoxy resin obtains low elastic modulus electrolyte.
The beneficial effects of the invention are as follows：The present invention is prepared for the lithium ion battery with multilayer electrolyte structure, the electrolysis
Matter has higher electrical conductivity, and 10 can be more than at room temperature-4S/cm, and elastic modelling quantity is more 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
Elastic modelling quantity electrolyte can keep solid electrolyte fully to be contacted with battery plus-negative plate, interface impedance be reduced, in cyclic process
The middle increase for suppressing the internal resistance of cell, improves the cycle life and specific capacity of battery.Meanwhile, the battery applications lithium an- ode is improved
The specific capacity of battery；It is likely to be brought into close contact between solid electrolyte and electrode and causes interface impedance, increases the interior of battery
Resistance, reduces the capacity of battery, by multilayer electrolyte structure, makes and fabulous contact is resulted between electrode and electrolyte, carry
The charging and discharging capabilities of high battery.Meanwhile, with the circulation of battery, the volume of electrode can also change, and cause electrode and solid-state
The separation of electrolyte, triggers capacity to decline, using multilayer electrolyte, the small electrolyte of elastic modelling quantity can become with electrode volume
Change and change, remain the close contact of electrode and electrolyte.Thus the lithium battery of forecast scheme configuration has specific capacity high, safety
Good, the characteristics of cycle life is good of property.
Brief description of the drawings
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.
Embodiment
Embodiment 1
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）LiMn2O4 is coated on aluminium foil, the positive pole lamella of battery is formed；
（3）By LiPF6It is well mixed to obtain low elastic modulus in the mixed solvent for being dissolved in propene carbonate and ethylene carbonate
Electrolyte（Liquid electrolyte）, LiPF6Concentration be 1mol/L；
（4）Polyphenylene sulfide is mixed with LiTFSI, 300 DEG C of holding 12h is heated to, is cooled to after room temperature and is broken into mixture
Grain, is extruded into roll film by particle in the case where temperature is 300 DEG C using extruder, is cooled to room temperature；Tetrachloroquinone is dissolved in two
Maceration extract is obtained in the ring of oxygen six, obtained roll film is put into maceration extract afterwards, airtight heating 30h, is obtained at 60 DEG C
High elastic modulus dielectric substrate；The mass ratio of polyphenylene sulfide, LiTFSI and tetrachloroquinone is 10：2：1；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 12h at 60 DEG C, is obtained 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 for the use individual 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 of application lithium an- ode, the cycle life of MULTILAYER COMPOSITE solid electrolyte than
Common barrier film liquid electrolyte lithium battery length is a lot, and the safety problems such as internal short-circuit does not occur after hundreds of 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, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）LiMn2O4 is coated on aluminium foil, the positive pole lamella of battery is formed；
（3）It is well mixed to obtain low elasticity mould in the mixed solvent that LiTFSI is dissolved in propene carbonate and diethyl carbonate
Measure electrolyte（Liquid electrolyte）, LiTFSI concentration is 0.7mol/L；
（4）Polyphenylene oxide is mixed with LiTFSI, 310 DEG C of holding 10h is heated to, is cooled to after room temperature and is broken into mixture
Grain, is extruded into roll film by particle in the case where temperature is 310 DEG C using extruder, is cooled to room temperature；Dichlorodicyanobenzoquinone is molten
Maceration extract is obtained in dioxane, obtained roll film is put into maceration extract afterwards, the airtight heating 25h at 80 DEG C,
Obtain high elastic modulus dielectric substrate；The mass ratio of polyphenylene oxide, LiTFSI and dichlorodicyanobenzoquinone is 10：3：2；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 10h at 65 DEG C, is obtained lithium battery.
Embodiment 3
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）Lithium titanate is coated on aluminium foil, the positive pole lamella of battery is formed；
（3）It is well mixed to obtain low elastic modulus in the mixed solvent that LiFSI is dissolved in ethylene carbonate and dimethyl carbonate
Electrolyte（Liquid electrolyte）, LiFSI concentration is 1.0mol/L；
（4）Polyphenylene sulfide is mixed with LiFSI, 320 DEG C of holding 8h is heated to, is cooled to after room temperature and is broken into mixture
Grain, is extruded into roll film by particle in the case where temperature is 320 DEG C using extruder, is cooled to room temperature；Tetracyanoethylene is dissolved in two
Maceration extract is obtained in the ring solvent of oxygen six, obtained roll film is put into maceration extract afterwards, the airtight heating 22h at 120 DEG C,
Obtain high elastic modulus electrolyte；The mass ratio of polyphenylene sulfide, LiFSI and tetracyanoethylene is 10：4：4；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 8h at 70 DEG C, is obtained lithium battery.
Embodiment 4
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）Phosphorus is coated on aluminium foil, the positive pole lamella of battery is formed；
（3）In the mixed solvent that LiFNFSI is dissolved in diethyl carbonate and dimethyl carbonate, liquid electrolyte is well mixed,
LiFNFSI concentration is 1.2mol/L, and epoxy resin is added into liquid electrolyte（Bisphenol A type epoxy resin）, epoxy resin
Addition be liquid electrolyte quality 15%, obtain low elastic modulus electrolyte；
（4）Polyphenylene oxide is mixed with LiFNFSI, 330 DEG C of holding 6h is heated to, is cooled to after room temperature and is broken into mixture
Grain, is extruded into roll film by particle in the case where temperature is 330 DEG C using extruder, is cooled to room temperature；By four cyano to secondary first
Base benzoquinones, which is dissolved in dioxane, obtains maceration extract, and obtained roll film is put into maceration extract afterwards, closed at 150 DEG C
15h is heated, high elastic modulus dielectric substrate is obtained；Polyphenylene oxide, LiFNFSI and four cyano are to the mass ratio of secondary methylbenzoquinone
10：5：5；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 5h at 75 DEG C, is obtained lithium battery.
Embodiment 5
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）Many lithium sulfides are coated on aluminium foil, the positive pole lamella of battery is formed；
（3）By LiClO4In the mixed solvent for being dissolved in propene carbonate and dimethyl carbonate, LiClO4Concentration be 0.7mol/
L, obtains liquid electrolyte, and acrylate is added into liquid electrolyte（Ethoxyquin tetramethylol methane tetraacrylate）, mixing is
It is even to obtain low elastic modulus electrolyte（Gel electrolyte）, acrylate（Ethoxyquin tetramethylol methane tetraacrylate）Addition
For the 1% of liquid electrolyte quality；
（4）Polyphenylene sulfide is mixed with LiOH, 340 DEG C of holding 4h is heated to, is cooled to after room temperature and mixture is broken into particle,
Particle is extruded into roll film in the case where temperature is 340 DEG C using extruder, room temperature is cooled to；Oxygen molecule is dissolved in dioxane
Maceration extract is obtained in solvent, obtained roll film is put into maceration extract afterwards, airtight heating 10h, obtains height at 170 DEG C
Elastic modelling quantity dielectric substrate；The mass ratio of polyphenylene sulfide, LiOH and oxygen molecule is 10：6：7；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 0.5h at 80 DEG C, is obtained lithium battery.
Embodiment 6
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）LiFePO4 is coated on aluminium foil, the positive pole lamella of battery is formed；
（3）By LiClO4In the mixed solvent for being dissolved in propene carbonate and diethyl carbonate, LiClO4Concentration be 1.5mol/
L, obtains liquid electrolyte, and fluoropolymer is added into liquid electrolyte, well mixed to obtain low elastic modulus electrolyte（It is solidifying
Glue electrolyte）, the addition of fluoropolymer is the 30% of liquid electrolyte quality；
（4）Polyphenylene oxide is mixed with LiOH, 350 DEG C of holding 0.5h is heated to, is cooled to after room temperature and mixture is broken into particle,
Particle is extruded into roll film in the case where temperature is 350 DEG C using extruder, room temperature is cooled to；Tetracyanoethylene is dissolved in dioxy six
Maceration extract is obtained in ring solvent, obtained roll film is put into maceration extract afterwards, airtight heating 15h, is obtained at 150 DEG C
High elastic modulus electrolyte；The mass ratio of polyphenylene oxide, LiOH and tetracyanoethylene is 10：8：10；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 12h at 70 DEG C, is obtained lithium battery.
Embodiment 7
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）By nickel-cobalt-manganese ternary material（NCM622）It is coated on aluminium foil, forms the positive pole lamella of battery；
（3）By LiClO4With the well mixed lithium ion and asphalt mixtures modified by epoxy resin obtained in low elastic modulus electrolyte, lithium salts of epoxy resin
The mol ratio of oxygen atom in fat is 1：4；
（4）Polyphenylene sulfide is mixed with LiOH, 320 DEG C of holding 8h is heated to, is cooled to after room temperature and mixture is broken into particle,
Particle is extruded into roll film in the case where temperature is 300 DEG C using extruder, room temperature is cooled to；Tetrachloroquinone is dissolved in dioxy six
Maceration extract is obtained in ring, obtained roll film is put into maceration extract afterwards, the airtight heating 15h at 150 DEG C obtains high-elastic
Property modulus dielectric substrate；The mass ratio of polyphenylene sulfide, LiOH and tetrachloroquinone is 10：7：5；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 8h at 70 DEG C, is obtained lithium battery.
Embodiment 8
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）By nickel cobalt aluminium ternary material（NCA）It is coated on aluminium foil, forms the positive pole lamella of battery；
（3）By LiClO4And epoxy resin（Polyethyleneglycol diglycidylether）It is well mixed to obtain low elastic modulus electrolyte,
The mol ratio of the oxygen atom in lithium ion and epoxy resin in lithium salts is 1：10；
（4）Polyphenylene oxide is mixed with LiOH, 320 DEG C of holding 10h is heated to, is cooled to after room temperature and mixture is broken into particle,
Particle is extruded into roll film in the case where temperature is 330 DEG C using extruder, room temperature is cooled to；Dichlorodicyanobenzoquinone is dissolved in two
Maceration extract is obtained in the ring solvent of oxygen six, obtained roll film is put into maceration extract afterwards, the airtight heating 20h at 180 DEG C,
Obtain high elastic modulus dielectric substrate；The mass ratio of polyphenylene oxide, LiOH and dichlorodicyanobenzoquinone is 10：3：8；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 10h at 75 DEG C, is obtained lithium battery.
Embodiment 9
The present embodiment proposes a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, and the lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Preparation process is as follows：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）By nickel cobalt aluminium ternary material（NCA）It is coated on aluminium foil, forms the positive pole lamella of battery；
（3）By LiTFSI and epoxy resin（Polypropylene glycol diglycidyl ether）It is well mixed to obtain low elastic modulus electrolyte,
The mol ratio of the oxygen atom in lithium ion and epoxy resin in lithium salts is 1：20；
（4）Polyphenylene oxide is mixed with LiTFSI, 320 DEG C of holding 10h is heated to, is cooled to after room temperature and is broken into mixture
Grain, is extruded into roll film by particle in the case where temperature is 330 DEG C using extruder, is cooled to room temperature；Dichlorodicyanobenzoquinone is molten
Maceration extract is obtained in dioxane solvent, obtained roll film is put into maceration extract afterwards, the airtight heating at 180 DEG C
20h, obtains high elastic modulus dielectric substrate；The mass ratio of polyphenylene oxide, LiTFSI and dichlorodicyanobenzoquinone is 10：3：8；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 10h at 75 DEG C, is obtained lithium battery.
Claims (8)
1. a kind of preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries, it is characterised in that：The lithium battery is wrapped successively from top to bottom
Include positive pole lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative plate
Layer；Comprise the following steps that：
（1）Lithium metal is fitted on Copper Foil by way of plating or roll-in, the negative pole lamella of battery is formed；
（2）Positive electrode active materials are coated on aluminium foil, the positive pole lamella of battery is formed；
（3）Lithium salts is dissolved in organic solvent or is well mixed lithium salts with epoxy resin and obtains low elastic modulus electrolyte；
（4）High molecular polymer is mixed with lithium salts, 300-350 DEG C of holding 0.5-12h is heated to, being cooled to after room temperature will mixing
Thing is broken into particle, and particle is extruded into roll film in the case where temperature is 300-350 DEG C using extruder, room temperature is cooled to；Will
Electron acceptor, which is dissolved in dioxane, obtains maceration extract, obtained roll film is put into maceration extract afterwards, at 60-200 DEG C
Lower airtight heating 1-30h, obtains high elastic modulus dielectric substrate；
（5）By step（1）Obtained negative pole lamella, step（2）Obtained positive pole lamella and step（4）Obtained high elastic modulus
Dielectric substrate is laminated, backward negative plate layer and high elastic modulus dielectric substrate between implantation step（3）Obtained low bullet
Property modulus electrolyte, form low elastic modulus dielectric substrate I, walked to being injected between positive pole lamella and high elastic modulus dielectric substrate
Suddenly（3）Obtained low elastic modulus electrolyte, low elastic modulus dielectric substrate II is formed, be followed successively by positive pole after stacking from top to bottom
Lamella, low elastic modulus dielectric substrate I, high elastic modulus dielectric substrate, low elastic modulus dielectric substrate II, negative pole lamella, layer
Poststack is sealed, and is heated 0.5-12h at 60-80 DEG C, is obtained lithium battery.
2. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that：The step
（2）In positive electrode active materials be nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4, lithium titanate, phosphorus, sulphur, many 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 step（4）Middle 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）In organic solvent be propene carbonate, ethylene carbonate, diethyl carbonate or dimethyl carbonate in any two kinds of groups
Close.
5. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that：The step
（4）Middle 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）The mass ratio of middle high molecular polymer, lithium salts and electron acceptor is 10：（2-8）：（1-10）.
7. the preparation method of MULTILAYER COMPOSITE electrolyte lithium batteries according to claim 1, it is characterised in that：The step
（3）It is liquid electrolyte that lithium salts is dissolved in the low elastic modulus electrolyte obtained in organic solvent, 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, third is added
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）In lithium salts and epoxy resin according to lithium ion and oxygen atom mol ratio be 1：（4-20）, lithium salts is mixed with epoxy resin
Conjunction uniformly obtains low elastic modulus electrolyte.
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| CN109802171A (en) * | 2018-12-15 | 2019-05-24 | 华南理工大学 | A kind of lithium ion battery interlayer solid electrolyte and preparation method thereof |
| CN110993934A (en) * | 2019-11-08 | 2020-04-10 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Lithium primary battery with lithium titanate anode and metal lithium cathode and preparation method thereof |
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| CN110993934A (en) * | 2019-11-08 | 2020-04-10 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Lithium primary battery with lithium titanate anode and metal lithium cathode and preparation method thereof |
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| CN112086678A (en) * | 2020-09-30 | 2020-12-15 | 合肥国轩高科动力能源有限公司 | Solid electrolyte, preparation method thereof and solid battery |
| CN112448028A (en) * | 2020-12-12 | 2021-03-05 | 安徽嘉誉伟丰机电科技有限公司 | Preparation method of stable electrolyte suitable for secondary lithium battery |
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