CN109802174B - Preparation and application of polycarbonate-based polymer electrolyte - Google Patents
Preparation and application of polycarbonate-based polymer electrolyte Download PDFInfo
- Publication number
- CN109802174B CN109802174B CN201910024056.3A CN201910024056A CN109802174B CN 109802174 B CN109802174 B CN 109802174B CN 201910024056 A CN201910024056 A CN 201910024056A CN 109802174 B CN109802174 B CN 109802174B
- Authority
- CN
- China
- Prior art keywords
- lithium
- polymer electrolyte
- mass
- electrolyte
- ethylene carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
PolymerThe preparation of carbonate-based polymer electrolyte and its application belong to the technical field of lithium ion battery. The invention uses ethylene carbonate, conductive lithium salt, porous support material and solvent to prepare polymer electrolyte. The preparation process of the polymer electrolyte is simple and easy to control, and has excellent mechanical properties; the thickness is 50-500 μm; room temperature ionic conductivity > 10‑3S cm‑1The electrochemical window is more than 4.7V; the polymer electrolyte can effectively inhibit the growth of dendritic crystals of the lithium negative electrode, and improve the compatibility with an interface and the long cycle performance; the solid-state lithium ion battery can work for a long time at room temperature. Meanwhile, the polymer electrolyte has good flexibility and is also suitable for flexible lithium ion battery devices of wearable electronic equipment.
Description
Technical Field
The invention relates to the field of polymer electrolytes for lithium ion batteries, in particular to a preparation method of a novel polycarbonate-based polymer electrolyte and application of the novel polycarbonate-based polymer electrolyte in a solid lithium ion battery, belonging to the technical field of lithium ion batteries.
Background
In recent years, lithium ion batteries have become increasingly widely used due to their high energy density and high reliability. However, commercial batteries mostly use conventional organic liquid electrolytes, such as ethylene carbonate, propylene carbonate, and the like. The further popularization and application of lithium ion batteries are seriously hindered due to the safety defects of high chemical activity, volatility, easiness in ignition, explosion and the like of the organic electrolyte. In addition, when the negative electrode is made of metal lithium, lithium dendrite is generated on the surface of the metal lithium along with the continuous insertion and extraction of lithium ions in the middle working process of the liquid battery. The formation of lithium dendrites not only causes the occurrence of dead lithium regions, which degrades the cycle performance of the battery, but also pierces the separator, which causes short-circuiting of the battery, severely limiting the development and application of high energy density lithium metal batteries. Therefore, the development of a solid electrolyte to replace the traditional liquid electrolyte has epoch-making significance for the development of the lithium metal battery with high energy density. The polymer electrolyte has been widely accepted due to the advantages of good compatibility with lithium metal, high thermal stability, simple preparation process, good flexibility, adjustable shape and size and the like. An ideal polymer electrolyte should possess the following advantages: 1. approaching the ionic conductivity of the liquid electrolyte; 2. the electrode has good compatibility with the electrode; 3. a wide electrochemical window; 4. the preparation process is simple. However, it has been difficult to satisfy the above-mentioned advantages simultaneously with the polymer electrolyte.
Polyethylene oxide (PEO), reported by Wright et al in 1973, and confirmed by Armand in 1979, and proposed as an electrolyte material for solid-state batteries, has advanced the research of polymer electrolytes into a new development stage. But because the PEO-based polymer electrolyte has low ionic conductivity at room temperature (the PEO room temperature conductivity is about 10)-7Scm-1) And a lower electrochemical stability window, which cannot meet the market demand and can not be widely used and popularized. Although many scholars have physically modified PEO (blending, adding plasticizer) and chemically modified PEO (graft modification), the ionic conductivity of PEO can be improved to some extent (room temperature can reach 10 deg.C)-5～10-4S cm-1) But still suffer from low electrochemical window and interface problems. Therefore, many researchers have been working on developing polymer electrolytes containing highly polar carbonate groups [ -O- (C ═ O) -O-]Polymers have attracted considerable attention from researchers. The patent No. CN105591154A provides a polycarbonate all-solid-state polymer electrolyte, the room-temperature ionic conductivity of the polymer electrolyte is 2 x 10-5S cm-1～1×10-3S cm-1The electrochemical window is greater than 4V. In addition, patent No. CN 105702919a provides a method for preparing an electrode for a lithium battery comprising an interface-stable polymer material and its application in a solid-state lithium battery. The polymer electrolyte is prepared by adopting the poly (ethylene carbonate) (PVCA) or the copolymer thereof, a covering film can be formed on the surface of an electrode, and the damage of the electrode material and the decomposition of the solid electrolyte on the surfaces of a positive electrode and a negative electrode in the charge-discharge process can be effectively inhibited. The two carbonate-based polymer electrolytes have high ionic conductivity and good interface stability, but have low electrochemical window (less than 4.7V), and are not suitable for being applied to a high-nickel cathode material system.
In view of the above problems, we have developed a novel polycarbonate-based polymer electrolyte prepared using ethylene carbonate, lithium salt, a porous support material, and a solvent. The preparation process of the polymer electrolyte is simple and easy to control, and has excellent mechanical properties; room temperature ionic conductivity > 10-3S cm-1Electrochemical window >4.7V; the polymer electrolyte can effectively inhibit the growth of dendritic crystals of the lithium negative electrode, and improve the compatibility with an interface and the long cycle performance; the solid-state lithium ion battery can work for a long time at room temperature. Meanwhile, the polymer electrolyte has good flexibility and is also suitable for flexible lithium ion battery devices of wearable electronic equipment.
Disclosure of Invention
The invention aims to provide a preparation method of a novel polycarbonate-based polymer electrolyte and application of the novel polycarbonate-based polymer electrolyte in a solid lithium ion battery.
The technical scheme of the invention is as follows:
a novel polycarbonate-based polymer electrolyte, characterized in that: crosslinking a liquid mixture before curing, which comprises liquid ethylene carbonate, a conductive lithium salt and an organic solvent, wherein an initiator or a catalyst is further added, immersing the porous support material into the liquid mixture or coating the liquid mixture on the porous support material, and then curing to prepare a polymer electrolyte; wherein the composition of each substance in the liquid mixture is: the mass fraction of the ethylene carbonate accounts for 30-80% of the mixture, the mass fraction of the conductive lithium salt accounts for 10-50% of the mixture, the mass fraction of the organic solvent accounts for 1-50% of the mixture, and the mass fraction of the initiator (or catalyst) accounts for 0.5-5% of the mass of the ethylene carbonate.
The preparation of the novel polycarbonate-based polymer electrolyte is characterized in that the structure of ethylene carbonate is as follows:
the novel polycarbonate-based polymer electrolyte is characterized in that the conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (trifluoromethanesulfonyl) methide [ LiC (SO)2CF3)3]；
The organic solvent is one or more of the following solvents: n-methylpyrrolidone (NMP), ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1, 2-dimethoxyethane, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl sulfoxide;
the initiator or the catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN), dimethyl Azobisisobutyrate (AIBME), Benzoyl Peroxide (BPO), platinum water (Pt);
the porous supporting material is one or more of cellulose non-woven fabric, polyethylene non-woven fabric, polypropylene non-woven fabric, glass fiber non-woven fabric and polytetrafluoroethylene non-woven fabric.
The preparation method of the novel polycarbonate-based polymer electrolyte is characterized by comprising the following steps of: preparing ethylene carbonate, conductive lithium salt and organic solvent with corresponding mass fractions into electrolyte, and uniformly stirring; adding initiator or catalyst with corresponding mass fraction and stirring uniformly; coating or immersing the electrolyte into a polytetrafluoroethylene mould containing a porous support material, and heating and curing at 60-120 ℃ for 2-12 hours to form a film.
The polymer solid-state lithium ion battery containing the novel polycarbonate-based polymer electrolyte is characterized by comprising: a positive electrode, a negative electrode and the polymer electrolyte of the present invention which is placed between the positive electrode and the negative electrode and has the functions of a diaphragm and an electrolyte;
the polymer solid-state lithium-ion battery is characterized in that: the positive active material is lithium iron phosphate (LiFeO)4) Lithium Nickel Cobalt Aluminate (NCA), lithium rich materials (LLOs), lithium cobaltate (LiCoO)2) Lithium ion fluorophosphate, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium iron manganese phosphate, and lithium nickelate (LiNiO)2) One or more of the above; the negative active material is metal lithium, metal lithium alloy, carbon-silicon composite material, lithium titanate, graphite, lithium metal nitride, antimony oxide, carbon-germanium composite materialOne or more of a composite material and lithium titanium oxide.
The polymer solid-state lithium ion battery is characterized in that: the preparation of the positive electrode comprises the following steps: (1) the preparation method of the cathode material comprises the following steps: grinding and mixing a positive electrode active material accounting for 50-90% by mass and a conductive agent acetylene black accounting for 5-30% by mass, adding polyvinylidene fluoride (PVDF) accounting for 1-15% by mass, an electrolyte mixed solution accounting for 1-15% by mass and 1-methyl-2 pyrrolidone (NMP), grinding and mixing to obtain a positive electrode material, wherein the 1-methyl-2 pyrrolidone (NMP) is used for adjusting viscosity and is not counted in the mass percentage composition of the positive electrode material; (2) coating the anode material on the surface of the aluminum foil, and drying to obtain an anode;
the metal lithium and the metal lithium alloy can be directly used as corresponding negative electrodes;
or preparation of a negative electrode, comprising the steps of: (1) preparing a negative electrode material: grinding and mixing 30-80% by mass of a negative electrode active material and 5-30% by mass of a conductive agent acetylene black; adding polyvinylidene fluoride (PVDF) accounting for 5-25% of the mass fraction, electrolyte mixed liquor accounting for 1-15% of the mass fraction and 1-methyl-2-pyrrolidone (NMP) to be ground and mixed to obtain a negative electrode material; wherein, the 1-methyl-2 pyrrolidone (NMP) is used for adjusting the viscosity and is not counted in the mass percentage composition of the cathode material; (2) and coating the copper foil surface, and drying to obtain the cathode.
The electrolyte mixed liquid in the anode material and the cathode material comprises the following components: the electrolyte mixed liquid comprises 30-80% of ethylene carbonate by mass, 10-50% of conductive lithium salt by mass, 1-50% of organic solvent by mass and 0.5-5% of initiator or catalyst by mass; the specific selection range of each substance in the electrolyte solution mixture is the same as the selection range of each substance of the polycarbonate-based polymer electrolyte raw material described above.
The preparation process of the battery comprises the following steps of (1): ex-situ assembly processes-positive and negative electrodes and the solid polymer electrolytes described above; (2): and (3) in-situ assembly technology, namely injecting the electrolyte mixed solution into a battery system of a positive electrode, a diaphragm and a negative electrode, and curing at 60-120 ℃.
The invention has the innovativeness and practicability that:
the solid polymer electrolyte is prepared by the mixture of ethylene carbonate, conductive lithium salt, porous support material and organic solvent for the first time. The polymer electrolyte has high ionic conductivity (more than 10) at room temperature-3S cm-1) Electrochemical window (> 4.7V) and thermal stability. Meanwhile, when the polymer electrolyte is assembled into a solid lithium ion battery, a protective layer can be formed on the surface of a lithium battery electrode material and metal lithium, so that the damage of electrode crystals caused by the embedding and the separation of lithium ions can be effectively inhibited, and the long-cycle stability of the lithium battery is further improved. In addition, no organic solvent is added in the preparation process of the polymer electrolyte, and the polymer electrolyte is prepared by in-situ polymerization, so that potential safety hazards and environmental pollution are eliminated, and the safety and the practicability of the lithium battery are greatly improved. The method can be applied to all-solid-state lithium batteries (including lithium-sulfur batteries), all-solid-state lithium ion batteries and other secondary high-energy lithium batteries.
Drawings
Fig. 1 is a CV diagram in polymer electrolyte production example 2.
Fig. 2 shows the charge and discharge performance of the lithium ion battery in example 7 of the solid state lithium ion battery preparation.
Detailed Description
The present invention is illustrated below by specific examples, which are provided for better understanding of the present invention and are not intended to limit the scope of the present invention in any way.
Preparation of polymer electrolyte:
example 1
3g of ethylene carbonate and 0.8g of lithium bistrifluoromethanesulfonylimide (LiTFSI) were dissolved in 5ml of acetonitrile, and the mixture was stirred at room temperature to be completely dissolved; 0.1g of azobisisobutyronitrile was added thereto and stirred uniformly. On a polytetrafluoroethylene die, taking a whatman film as a porous supporting framework, and blade-coating the uniformly stirred mixture on two sides of the whatman film; heating the mixture in a vacuum drying oven at 80 ℃ for 10 hours to solidify and form a film.
Example 2
1g of ethylene carbonate and 0.25g of lithium bistrifluoromethanesulfonylimide (LiTFSI) were dissolved in 1.5ml of N-methylpyrrolidone (NMP), and the mixture was stirred at room temperature to completely dissolve the lithium bistrifluoromethanesulfonylimide (LiTFSI); 0.02g of azobisisobutyronitrile was added thereto and stirred uniformly. On a polytetrafluoroethylene die, taking a whatman film as a porous supporting framework, and blade-coating the uniformly stirred mixture on two sides of the whatman film; heating the mixture in a vacuum drying oven at 80 ℃ for 10 hours to solidify and form a film.
Example 3
1.38g of ethylene carbonate and 0.4g of lithium bistrifluoromethanesulfonylimide (LiTFSI) were dissolved in 1.5ml of N-methylpyrrolidone (NMP), and the mixture was stirred at room temperature to completely dissolve the lithium bistrifluoromethanesulfonylimide (LiTFSI); 0.02g of dibutyltin bis (acetylacetonate) was added thereto and the mixture was stirred uniformly. On a polytetrafluoroethylene die, taking a whatman film as a porous supporting framework, and blade-coating the uniformly stirred mixture on two sides of the whatman film; heating the mixture in a vacuum drying oven at 80 ℃ for 10 hours to solidify and form a film.
Example 4
1.8g of ethylene carbonate and 0.65g of lithium perchlorate (LiClO)4) Dissolving in 2ml tetrahydrofuran, stirring at room temperature to make it completely dissolve; 0.02g of dibutyltin bis (acetylacetonate) was added thereto and the mixture was stirred uniformly. On a polytetrafluoroethylene die, taking a whatman film as a porous supporting framework, and blade-coating the uniformly stirred mixture on two sides of the whatman film; heating the mixture in a vacuum drying oven at 80 ℃ for 10 hours to solidify and form a film.
Example 4
2.3g of ethylene carbonate and 0.8g of lithium perchlorate (LiClO)4) Dissolving in 2ml tetrahydrofuran, stirring at room temperature to make it completely dissolve; 0.05g of platinum water (Pt) was added thereto and stirred uniformly. On a polytetrafluoroethylene die, taking a whatman film as a porous supporting framework, and blade-coating the uniformly stirred mixture on two sides of the whatman film; heating the mixture in a vacuum drying oven at 80 ℃ for 10 hours to solidify and form a film.
Example 5
Dissolving 5g of ethylene carbonate and 1.23g of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 5ml of dimethyl sulfoxide, and stirring at room temperature to completely dissolve the ethylene carbonate and the lithium bistrifluoromethanesulfonylimide; 0.08g of platinum water (Pt) was added thereto and stirred uniformly. On a polytetrafluoroethylene die, taking a whatman film as a porous supporting framework, and blade-coating the uniformly stirred mixture on two sides of the whatman film; heating the mixture in a vacuum drying oven at 80 ℃ for 10 hours to solidify and form a film.
Thickness of electrolyte: the thickness of the block polymer electrolyte was measured using a micrometer (precision 0.01 mm), and 3 points on the film were arbitrarily removed for measurement, and the average value was determined.
Ionic conductivity: the impedance of the button cell of 2032 was measured by assembling two stainless steel gaskets sandwiching the polymer electrolyte according to the formula
Wherein L is the thickness of the polymer electrolyte, S is the area of the stainless steel gasket, and R is the measured resistance value.
Electrochemical window: clamping polymer electrolyte by stainless steel and lithium sheets, assembling 2032 button cell, and performing linear volt-ampere scanning measurement at initial voltage of 2.8V, maximum potential of 5.5V and scanning speed of 1mV S-1。
Preparing a solid lithium ion battery: the specific composition of the electrolyte mixture used in the following examples is the same as the corresponding solid polyelectrolyte component.
Example 6
Uniformly grinding 80mg of nickel cobalt lithium aluminate and 15mg of acetylene black serving as a conductive agent for 40 min; adding 5mg of binder polyvinylidene fluoride, 3mg of electrolyte mixed solution and 160 mu L of 1-methyl-2 pyrrolidone, and uniformly grinding for 40 min; coating on the surface of an aluminum foil, and drying for 8 hours at 80 ℃ under a vacuum condition; the electrode sheet was cut into a circular sheet of R0.6 mm, and the polymer electrolyte of example 1 was used to prepare a solid-state lithium ion half cell, and then metal lithium was used as a negative electrode.
Example 7
Uniformly grinding 240mg of lithium iron phosphate and 45mg of acetylene black serving as a conductive agent for 40 min; adding 15mg of binder polyvinylidene fluoride, 15mg of electrolyte mixed solution and 150 mu L of 1-methyl-2 pyrrolidone, and uniformly grinding for 40 min; coating on the surface of an aluminum foil, and drying for 8 hours at 80 ℃ under a vacuum condition; the electrode sheet was cut into a circular sheet with an R of 0.6mm, and the solid-state lithium ion half cell was assembled using the above polymer electrolyte. Then, metallic lithium was used as a negative electrode.
Example 8
Uniformly grinding 250mg of nickel cobalt lithium aluminate and 46.8mg of acetylene black serving as a conductive agent for 40 min; adding 15mg of binder polyvinylidene fluoride, 15mg of electrolyte mixed solution and 150 mu L of 1-methyl-2 pyrrolidone, and uniformly grinding for 40 min; coating on the surface of an aluminum foil, and drying for 8 hours at 80 ℃ under a vacuum condition; the electrode sheet was cut into a circular sheet with an R of 0.6mm, and the solid-state lithium ion half cell was assembled using the above polymer electrolyte. Then, metallic lithium was used as a negative electrode.
Claims (9)
1. A polycarbonate-based polymer electrolyte, characterized in that: crosslinking a liquid mixture before curing, which comprises liquid ethylene carbonate, a conductive lithium salt and an organic solvent, wherein an initiator or a catalyst is further added, immersing the porous support material into the liquid mixture or coating the liquid mixture on the porous support material, and then curing to prepare a polymer electrolyte; wherein the composition of each substance in the liquid mixture is: the mass fraction of the ethylene carbonate accounts for 30-80% of the mixture, the mass fraction of the conductive lithium salt accounts for 10-50% of the mixture, the mass fraction of the organic solvent accounts for 1-50% of the mixture, and the mass fraction of the initiator or the catalyst accounts for 0.5-5% of the mass of the ethylene carbonate;
the structure of the ethylene carbonate is as follows:
the polymer electrolyte has an ionic conductivity of > 10 at room temperature-3S cm-1Electrochemical deviceThe study window is > 4.7V.
2. A polycarbonate-based polymer electrolyte according to claim 1, wherein: the conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (trifluoromethanesulfonyl) methide [ LiC (SO)2CF3)3]。
3. A polycarbonate-based polymer electrolyte according to claim 1, wherein: the organic solvent is one or more of the following: n-methylpyrrolidone (NMP), ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1, 2-dimethoxyethane, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl sulfoxide; the initiator or catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), Azobisisoheptonitrile (ABVN), Azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME), Benzoyl Peroxide (BPO), platinum water (Pt).
4. A polycarbonate-based polymer electrolyte according to claim 1, wherein: the porous supporting material is one or more of cellulose non-woven fabric, polyethylene non-woven fabric, polypropylene non-woven fabric, glass fiber non-woven fabric and polytetrafluoroethylene non-woven fabric.
5. A method for preparing the polycarbonate-based polymer electrolyte according to any one of claims 1 to 4, comprising the steps of: preparing ethylene carbonate, conductive lithium salt and organic solvent with corresponding mass fractions into electrolyte, and uniformly stirring; adding initiator or catalyst with corresponding mass fraction and stirring uniformly; coating or immersing the electrolyte into a polytetrafluoroethylene mould containing a porous support material, and heating and curing at 60-120 ℃ for 2-12 hours to form a film.
6. A polymer solid state lithium ion battery comprising the polycarbonate-based polymer electrolyte according to any one of claims 1 to 4, comprising: a positive electrode, a negative electrode and a polymer electrolyte which is arranged between the positive electrode and the negative electrode and has the functions of a diaphragm and an electrolyte.
7. The polymer solid state lithium ion battery of claim 6, wherein: the anode active material is lithium iron phosphate LiFeO4Lithium nickel cobalt aluminate NCA, lithium rich materials LLOs, lithium cobaltate LiCoO2Lithium ion fluorophosphate, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide, lithium iron manganese phosphate, and lithium nickel oxide LiNiO2One or more of the above; the negative active material is one or more of metal lithium, metal lithium alloy, carbon-silicon composite material, graphite, lithium metal nitride, antimony oxide, carbon-germanium composite material and lithium-titanium oxide;
the preparation of the positive electrode comprises the following steps: (1) the preparation method of the cathode material comprises the following steps: grinding and mixing a positive electrode active material accounting for 50-90% by mass and a conductive agent acetylene black accounting for 5-30% by mass, adding polyvinylidene fluoride (PVDF) accounting for 1-15% by mass, an electrolyte mixed solution accounting for 1-15% by mass and 1-methyl-2 pyrrolidone (NMP), grinding and mixing to obtain a positive electrode material, wherein the 1-methyl-2 pyrrolidone (NMP) is used for adjusting viscosity and is not counted in the mass percentage composition of the positive electrode material; (2) coating the anode material on the surface of the aluminum foil, and drying to obtain an anode;
the metal lithium and the metal lithium alloy can be directly used as corresponding negative electrodes;
or preparation of a negative electrode, comprising the steps of: (1) preparing a negative electrode material: grinding and mixing 30-80% by mass of a negative electrode active material and 5-30% by mass of a conductive agent acetylene black; adding polyvinylidene fluoride (PVDF) accounting for 5-25% of the mass fraction, electrolyte mixed liquor accounting for 1-15% of the mass fraction and 1-methyl-2-pyrrolidone (NMP) to be ground and mixed to obtain a negative electrode material; wherein, the 1-methyl-2 pyrrolidone (NMP) is used for adjusting the viscosity and is not counted in the mass percentage composition of the cathode material; (2) and coating the copper foil surface, and drying to obtain the cathode.
8. The polymeric solid state lithium ion battery of claim 7, wherein: the electrolyte mixed liquid in the anode material and the cathode material comprises the following components: the electrolyte mixed liquid comprises 30-80% of ethylene carbonate by mass, 10-50% of conductive lithium salt by mass, 1-50% of organic solvent by mass and 0.5-5% of initiator or catalyst by mass; the specific selection range of each substance in the electrolyte solution mixture is the same as the selection range of each substance of the polycarbonate-based polymer electrolyte raw material.
9. The polymeric solid state lithium ion battery of claim 7, wherein: the preparation of the battery comprises the following two methods; (1): ex-situ assembly process-positive and negative electrodes and the solid polymer electrolyte of claim 5; (2): in-situ assembly process, the electrolyte mixture liquid of claim 8 is injected into a battery system of a positive electrode, a separator and a negative electrode, and is cured at 60-120 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910024056.3A CN109802174B (en) | 2019-01-10 | 2019-01-10 | Preparation and application of polycarbonate-based polymer electrolyte |
| PCT/CN2019/110925 WO2020143259A1 (en) | 2019-01-10 | 2019-10-14 | Preparation and application of polycarbonate-based polymer electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910024056.3A CN109802174B (en) | 2019-01-10 | 2019-01-10 | Preparation and application of polycarbonate-based polymer electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109802174A CN109802174A (en) | 2019-05-24 |
| CN109802174B true CN109802174B (en) | 2022-03-22 |
Family
ID=66557122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910024056.3A Active CN109802174B (en) | 2019-01-10 | 2019-01-10 | Preparation and application of polycarbonate-based polymer electrolyte |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109802174B (en) |
| WO (1) | WO2020143259A1 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109802174B (en) * | 2019-01-10 | 2022-03-22 | 北京工业大学 | Preparation and application of polycarbonate-based polymer electrolyte |
| CN112242560A (en) * | 2019-07-19 | 2021-01-19 | 中国科学院物理研究所 | Solid-state lithium battery and electrode-diaphragm layer interface improvement method and application thereof |
| EP3767728A1 (en) * | 2019-07-19 | 2021-01-20 | Total Se | Solid polymer electrolyte comprising a polyalkylene carbonate |
| CN110734517B (en) * | 2019-10-14 | 2022-05-17 | 北京工业大学 | Preparation and application of polycarbonate-based block polymer electrolyte |
| CN110690500A (en) * | 2019-10-14 | 2020-01-14 | 北京工业大学 | Polymer electrolyte with high voltage window |
| US20210194055A1 (en) * | 2019-12-20 | 2021-06-24 | Enevate Corporation | Solid-state polymer electrolyte for use in production of all-solid-state alkali-ion batteries |
| CN115136375A (en) * | 2020-02-18 | 2022-09-30 | 赢创运营有限公司 | Hybrid polymer electrolytes for in situ polymerization of high voltage lithium batteries |
| CN111416087B (en) * | 2020-03-18 | 2022-02-15 | 江苏厚生新能源科技有限公司 | Heat radiation cross-linking semi-solid lithium battery diaphragm and preparation method thereof |
| CN113707934B (en) * | 2020-05-22 | 2023-12-12 | 比亚迪股份有限公司 | Lithium battery and manufacturing method thereof |
| CN114069035A (en) * | 2020-08-07 | 2022-02-18 | 上海科技大学 | Solid polymer electrolyte and preparation method and application thereof |
| CN111834662B (en) * | 2020-08-31 | 2022-07-08 | 珠海冠宇电池股份有限公司 | Interface functional layer, preparation method thereof and lithium ion battery |
| CN114447417A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Modified inorganic fast ion conductor and preparation method and application thereof |
| CN112490587B (en) * | 2020-11-17 | 2024-02-13 | 欣旺达动力科技股份有限公司 | Composite electrolyte diaphragm, preparation method thereof and solid-state battery |
| CN114597498A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院宁波材料技术与工程研究所 | Ultrathin multilayer-structure composite polymer electrolyte material, preparation method thereof and all-solid-state lithium secondary battery |
| CN112510251B (en) * | 2020-12-15 | 2023-01-24 | 电子科技大学 | SiC-based all-solid-state lithium ion battery polymer electrolyte and preparation method thereof |
| CN112670483B (en) * | 2020-12-25 | 2022-07-05 | 合肥国轩高科动力能源有限公司 | Positive plate, positive polar plate and solid-state battery |
| CN112952127A (en) * | 2021-03-02 | 2021-06-11 | 厦门大学 | Thermal battery electrolyte with adjustable temperature and preparation method and application thereof |
| CN113471542A (en) * | 2021-05-17 | 2021-10-01 | 香港科技大学 | Solid-state lithium battery and preparation method thereof |
| CN113707935B (en) * | 2021-08-18 | 2023-08-08 | 电子科技大学 | Polyfluorinated polymer solid electrolyte material and preparation method thereof |
| CN114420929B (en) * | 2021-12-09 | 2023-11-03 | 万向一二三股份公司 | Preparation method of solid battery containing conductive polymer binder |
| WO2023115535A1 (en) * | 2021-12-24 | 2023-06-29 | 宁德时代新能源科技股份有限公司 | Electrode assembly and manufacturing method therefor, secondary battery, battery module, battery pack, and electrical device |
| CN114380930B (en) * | 2021-12-28 | 2022-09-27 | 广东马车动力科技有限公司 | Polymer electrolyte, preparation method thereof and battery |
| CN114497724B (en) * | 2022-01-20 | 2023-05-23 | 苏州大学张家港工业技术研究院 | Solid electrolyte and preparation method and application thereof |
| CN114335701A (en) * | 2022-02-23 | 2022-04-12 | 贵州梅岭电源有限公司 | Composite solid electrolyte membrane and preparation method thereof |
| CN114744289A (en) * | 2022-04-11 | 2022-07-12 | 湖南立方新能源科技有限责任公司 | Magnetic composite solid electrolyte membrane, preparation method and method for preparing solid lithium metal battery |
| CN114899359B (en) * | 2022-06-27 | 2023-06-09 | 中国科学院化学研究所 | Improved lithium/silicon/carbon composite negative electrode and preparation method thereof |
| CN115064777A (en) * | 2022-07-08 | 2022-09-16 | 福州大学 | Gel electrolyte for lithium metal and preparation method and application thereof |
| CN115241522B (en) * | 2022-08-04 | 2024-04-05 | 中国人民解放军军事科学院防化研究院 | Preparation method of lithium lanthanum zirconium oxygen-based composite solid electrolyte membrane |
| CN115882057B (en) * | 2022-09-23 | 2023-09-08 | 四川新能源汽车创新中心有限公司 | Electrolyte, solid-state battery and preparation method of solid-state battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103840198A (en) * | 2012-11-20 | 2014-06-04 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery gel polymer electrolyte and preparation method thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3603383B2 (en) * | 1995-04-12 | 2004-12-22 | ソニー株式会社 | Polymer solid electrolyte |
| JP4141151B2 (en) * | 2002-02-27 | 2008-08-27 | 三洋電機株式会社 | Gel-like nonaqueous electrolyte secondary battery |
| JP4286011B2 (en) * | 2003-01-24 | 2009-06-24 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery and manufacturing method thereof |
| JP2011171096A (en) * | 2010-02-18 | 2011-09-01 | Sony Corp | Nonaqueous electrolyte battery |
| US9627713B2 (en) * | 2013-03-29 | 2017-04-18 | NOHMs Technologies, Inc. | Composite electrolyte including polymeric ionic liquid matrix and embedded nanoparticles, and method of making the same |
| CN103647107B (en) * | 2013-11-28 | 2016-02-03 | 中国东方电气集团有限公司 | For the dielectric film and preparation method thereof of all-solid lithium-ion battery |
| CN105826603B (en) * | 2016-04-06 | 2018-06-19 | 中国科学院青岛生物能源与过程研究所 | A kind of polymerized thylene carbonate vinyl ester lithium ion battery polymer electrolyte and its preparation method and application |
| CN106299471A (en) * | 2016-09-19 | 2017-01-04 | 哈尔滨工业大学 | A kind of hybrid solid-state polymer dielectric and preparation method and application |
| CN108400380B (en) * | 2018-04-24 | 2021-01-29 | 珠海冠宇电池股份有限公司 | Preparation method of composite polymer electrolyte membrane and lithium ion battery |
| CN108550907B (en) * | 2018-06-05 | 2020-08-21 | 北京卫蓝新能源科技有限公司 | In-situ composite solid electrolyte and application thereof, all-solid-state battery and preparation method thereof |
| CN108878967A (en) * | 2018-06-14 | 2018-11-23 | 北京工业大学 | A kind of preparation of block polymer electrolyte and application |
| CN108808082B (en) * | 2018-08-15 | 2022-06-07 | 中南大学 | Polymer solid electrolyte for lithium ion battery and preparation method thereof |
| CN109802174B (en) * | 2019-01-10 | 2022-03-22 | 北京工业大学 | Preparation and application of polycarbonate-based polymer electrolyte |
-
2019
- 2019-01-10 CN CN201910024056.3A patent/CN109802174B/en active Active
- 2019-10-14 WO PCT/CN2019/110925 patent/WO2020143259A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103840198A (en) * | 2012-11-20 | 2014-06-04 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery gel polymer electrolyte and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109802174A (en) | 2019-05-24 |
| WO2020143259A1 (en) | 2020-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109802174B (en) | Preparation and application of polycarbonate-based polymer electrolyte | |
| US20220181684A1 (en) | Hybrid solid-liquid electrolyte lithium storage battery | |
| CN108493486B (en) | Preparation method of in-situ polymerization solid-state battery | |
| CN113130895B (en) | Solid-state lithium ion battery and preparation method thereof | |
| CN108604674A (en) | Anode of secondary cell, its manufacturing method and the lithium secondary battery comprising the anode | |
| CN110048158B (en) | In-situ polymerization double-layer polymer electrolyte membrane and preparation method and application thereof | |
| US8852814B2 (en) | Method for developing an electrochemical device | |
| CN112133961B (en) | Gel electrolyte precursor and application thereof | |
| CN111725559B (en) | Solid electrolyte, method for preparing the same, and lithium secondary solid battery | |
| CN110734517B (en) | Preparation and application of polycarbonate-based block polymer electrolyte | |
| WO2021189161A1 (en) | All solid-state electrolyte composite based on functionalized metal-organic framework materials for li thoum secondary battery and method for manufacturing the same | |
| CN112909318B (en) | Lithium ion secondary battery, method of manufacturing the same, and electronic and electric products including the same | |
| CN113131005A (en) | Polymer electrolyte membrane and preparation method thereof, and metal lithium battery and preparation method thereof | |
| CN110224173B (en) | Self-healing solid polymer electrolyte for lithium battery and preparation method thereof | |
| CN110690500A (en) | Polymer electrolyte with high voltage window | |
| CN115882061A (en) | Preparation and application of poly (rotaxane) polymer electrolyte | |
| CN113363573B (en) | Preparation method of solid electrolyte, solid electrolyte and all-solid-state battery | |
| CN113363556B (en) | All-solid-state lithium ion battery | |
| CN115020802A (en) | In-situ ultraviolet light curing nanofiber composite solid electrolyte and preparation method and application thereof | |
| CN116111181A (en) | Modified sulfide electrolyte and application thereof | |
| KR20110119054A (en) | Lithium polymer battery | |
| CN115000504A (en) | Preparation and application of polysulfonic acid lactone-based polymer electrolyte | |
| CN116111186A (en) | Carbonate-based polymer electrolyte with wide electrochemical window | |
| KR20150069060A (en) | All-solid polymer electrolyte film containing micro-particles and the all-solid lithium polymer battery thereof | |
| CN116111179A (en) | Wide-temperature high-pressure polyallylcarbonate-based polymer electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |