CN115483431B - Diaphragm-free solid lithium ion battery and preparation method thereof - Google Patents

Diaphragm-free solid lithium ion battery and preparation method thereof Download PDF

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CN115483431B
CN115483431B CN202210772970.8A CN202210772970A CN115483431B CN 115483431 B CN115483431 B CN 115483431B CN 202210772970 A CN202210772970 A CN 202210772970A CN 115483431 B CN115483431 B CN 115483431B
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electrolyte
lithium ion
ion battery
functional layer
positive electrode
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CN115483431A (en
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邱越
邱枫
夏瑶
朱高龙
华剑锋
李立国
戴锋
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Sichuan New Energy Vehicle Innovation Center Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2300/0085—Immobilising or gelification of electrolyte
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The application provides a diaphragm-free solid-state lithium ion battery and a preparation method thereof, and relates to the technical field of lithium ion batteries. The diaphragm-free solid-state lithium ion battery comprises: a positive electrode, a negative electrode, a functional layer and an in-situ cured electrolyte, wherein the electrolyte is positioned between the positive electrode and the negative electrode; the functional layer comprises a coating material with low electronic conductivity; the functional layer is located between the positive electrode and the electrolyte, and/or the functional layer is located between the negative electrode and the electrolyte. The preparation method comprises the following steps: preparing raw materials of the functional layer into slurry, and coating the slurry on the positive electrode and/or the negative electrode to obtain a positive electrode plate and/or a negative electrode plate; mixing the raw materials of the electrolyte to obtain a solid electrolyte precursor solution; and assembling the positive electrode plate and the negative electrode plate into a dry cell, injecting the solid electrolyte precursor solution, and curing in situ. The lithium ion battery can ensure higher safety without a diaphragm by combining the functional layer and the in-situ solidified electrolyte.

Description

Diaphragm-free solid lithium ion battery and preparation method thereof
Technical Field
The application relates to the technical field of lithium ion battery preparation, in particular to a diaphragm-free solid lithium ion battery and a preparation method thereof.
Background
With the development of modern society, the application of lithium ion batteries permeates into aspects of life of people, and the lithium ion batteries play an increasingly important role from small portable electric equipment to large electric automobiles and energy storage power stations. In recent years, research on lithium ion batteries has been mainly directed to a high energy density technical route, but the safety problem thereof has also become increasingly prominent. In particular, in recent years, the use of high-energy density high-nickel positive electrode materials and silicon-containing negative electrodes has further increased the energy density of lithium ion batteries, but has also resulted in a great deterioration in the safety thereof, severely impeding the further use of lithium ion batteries. Therefore, how to thoroughly solve the safety problem of the lithium ion battery while ensuring the high energy density of the lithium ion battery becomes the key point of industry research.
Lithium ion batteries currently commercialized employ conventional polymer separators and organic liquid electrolytes. Under the external factors such as overheating and needling, the polymer diaphragm is easy to collapse, so that the anode and the cathode in the battery are in direct contact, internal short circuit is caused to cause the battery to be overheated rapidly, and meanwhile, a series of side reactions between the anode and cathode materials and electrolyte can release a large amount of heat, so that the battery is out of control, and the lithium ion battery is ignited or even exploded. Researchers find that the safety problem can be improved to a certain extent by methods such as coating positive electrode material particles, modifying a high-temperature-resistant diaphragm, adding a flame-retardant electrolyte additive and the like, so that the thermal runaway of the lithium battery is delayed, but the effect is limited, and the cost is high. In addition, the non-combustible, non-flowable solid electrolyte is used to replace the combustible liquid organic electrolyte, so that most of the safety problems encountered by the traditional lithium ion battery can be eliminated. However, the existing solid electrolyte has high cost, large preparation difficulty and serious interface problem, and is difficult to apply on a large scale.
Therefore, it is desirable to develop a solid state lithium battery that can match existing lithium ion battery manufacturing processes, greatly reducing costs, while improving the overheat and needling safety performance of the battery.
Disclosure of Invention
The purpose of the application is to provide a diaphragm-free solid-state lithium ion battery and a preparation method thereof.
In order to achieve the above object, the technical scheme of the present application is as follows:
a separator-less solid state lithium ion battery comprising: a positive electrode, a negative electrode, a functional layer, and an in-situ cured electrolyte, the electrolyte being located between the positive electrode and the negative electrode;
the functional layer is located between the positive electrode and the electrolyte, and/or the functional layer is located between the negative electrode and the electrolyte;
the functional layer comprises a coating material with an electronic insulation function.
Preferably, the composition of the functional layer comprises 70% -90% of the coating material and 10% -30% of the binder in percentage by mass, and the thickness of the functional layer is 20-50 μm;
preferably, the coating material comprises a porous material or a solid electrolyte material;
the binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber and cellulose.
Preferably, the porous material comprises any one of magnesia, zirconia, silica, titania and alumina, the particle size of the porous material is 1 μm-20 μm, and the pore diameter is 10nm-100nm;
preferably, the solid electrolyte material comprises perovskite electrolyte Li 0.33 La 0.557 TiO 3 Garnet-type electrolyte Li 7 La 3 Zr 2 O 12 Fast ion conductor Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 And L i2 S-P 2 S 5 Any one of the sulfide-based electrolytes.
Preferably, the electrolyte comprises, in mass percent, 5% -50% of a polymeric monomer, 0-10% of a fast ion conductor additive, 50-95% of a solvent, an initiator, and a lithium salt;
the mass of the initiator is 0.05% -1% of the total mass of the polymerization monomers;
the concentration of the lithium salt in the polymerization precursor solution formed by mixing the polymerization monomer, the fast ion conductor additive, the initiator and the solvent is 0.1mol/L to 3mol/L.
Preferably, the polymeric monomer comprises at least one of methyl methacrylate, vinylene carbonate, ethyl methacrylate, methoxypolyethylene glycol acrylate, glycidyl methacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylpropane triacrylate, ethylene glycol diacrylate, ethylene carbonate, ethylene oxide, and 1, 3-dioxolane;
preferably, the fast ion conductor additive comprises Li 6.4 Al 0.24 La 3 Zr 2 O 12 、Li 7 La 3 Zr 2 O 12 And succinonitrile, and at least one of succinonitrile;
preferably, the solvent comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, gamma-butyrolactone, methyl formate, dimethoxymethane and acetonitrile;
preferably, the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl, dicumyl peroxide, dibenzoyl peroxide and ammonium persulfate;
preferably, the lithium salt includes at least one of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethylsulfonimide, lithium tetrafluoroborate, and lithium hexafluoroarsenate.
Preferably, the positive electrode and the negative electrode include a current collector and an electrode layer, respectively;
the functional layer is located between the electrode layer and the electrolyte.
The application also provides a preparation method of the diaphragm-free solid lithium ion battery, which comprises the following steps: preparing the raw materials of the functional layer into slurry, and coating the slurry on the positive electrode and/or the negative electrode to obtain a positive electrode plate and/or a negative electrode plate;
mixing the raw materials of the electrolyte to obtain a solid electrolyte precursor solution;
and assembling the positive electrode plate and the negative electrode plate into a dry battery core, injecting the solid electrolyte precursor solution, and carrying out in-situ solidification to obtain the diaphragm-free solid lithium ion battery.
Preferably, the slurry is prepared by mixing a coating material of the functional layer, a binder and a slurry solvent;
the slurry solvent comprises at least one of dimethylformamide, dimethylacetamide, diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran;
the mass of the slurry solvent accounts for 50% -90% of the total mass of the slurry.
Preferably, after the coating, a drying treatment is also required, and the drying temperature is 60-110 ℃;
preferably, when the positive electrode and the negative electrode include a current collector and an electrode layer, respectively, the coating means coating on the surface of the electrode layer of the positive electrode and/or the surface of the electrode layer of the negative electrode.
Preferably, before the in-situ solidification, sealing and standing the dry cell injected with the solid electrolyte precursor solution;
and in the in-situ curing, heating and curing the battery after standing at the temperature of 40-85 ℃ for 2-12 h.
The beneficial effects of this application:
in the diaphragm-free solid-state lithium ion battery, the functional layer and the in-situ cured electrolyte are combined, so that on one hand, the electronic insulation performance of the functional layer is utilized, the contact short circuit between the anode and the cathode can be prevented, the diaphragm in the traditional lithium ion battery can be omitted, and the assembly difficulty of the solid-state battery is reduced; on the other hand, by utilizing the in-situ solidified electrolyte, no flowable liquid in the electrolyte can be ensured, and the needling safety of the battery can be greatly improved, so that the lithium ion battery has higher safety.
Furthermore, the functional layer has good mechanical property and structural stability, and can avoid side reaction under overheat condition, thereby improving the thermal safety of the battery; the functional coating has low density characteristic, and can not obviously reduce the energy density of the battery; the functional layer has electron insulation but does not affect the lithium ion transmission path, and the in-situ cured electrolyte also has high lithium ion conductivity, so that the electrochemical performance of the battery is not reduced.
In the preparation method of the diaphragm-free solid-state lithium ion battery, the used process is simple and convenient, the cost can be effectively controlled, meanwhile, the liquid injection process which is the same as the existing industrialized lithium ion battery is used for being led into the battery dry cell, the compatibility with the existing process is high, and the method is suitable for large-scale production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope of the present invention.
Fig. 1 is a schematic structural diagram of a non-separator solid state lithium ion battery of the present application.
Description of main reference numerals:
1-copper foil, 2-negative electrode layer, 3-negative electrode functional layer, 4-in-situ solidified electrolyte, 5-positive electrode functional layer, 6-positive electrode layer and 7-aluminum foil.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The application provides a no diaphragm solid-state lithium ion battery, includes: a positive electrode, a negative electrode, a functional layer, and an in-situ cured electrolyte, the electrolyte being located between the positive electrode and the negative electrode;
the functional layer comprises a coating material with an electronic insulation function;
the functional layer is located between the positive electrode and the electrolyte, and/or the functional layer is located between the negative electrode and the electrolyte. That is, the functional layer of the present application may be applied to the positive electrode alone, or to the negative electrode surface alone, or to both the positive electrode and the negative electrode surface.
In an alternative embodiment of the present application, the positive electrode and the negative electrode include a current collector and an electrode layer, respectively; the functional layer is located between the electrode layer and the electrolyte.
In the battery, the current collectors on the positive electrode and the negative electrode not only play a role of carrying active substances, but also collect electrons generated by electrochemical reaction to an external circuit, thereby realizing a process of converting chemical energy into electric energy. The current collector is one of indispensable component parts in the lithium ion battery, the current positive current collector applied to the production of the lithium ion battery core is aluminum foil, the negative current collector is copper foil, the aluminum foil is mainly rolled aluminum foil, and the copper foil is mainly electrolytic copper foil.
The positive electrode or negative electrode active material carried on the current collector may form a positive electrode layer or a negative electrode layer. Specifically, a positive electrode active material, a binder and a conductive agent are mixed into positive electrode slurry, and then coated on a positive electrode current collector, thereby forming a positive electrode layer. The positive electrode active material mainly comprises lithium iron phosphate, lithium nickelate, lithium cobaltate, lithium titanate, lithium-rich manganese, lithium nickel cobalt manganate, lithium nickel cobalt aluminate and the like. And mixing the anode active material, the binder and the conductive agent to form anode slurry, and coating the anode slurry on an anode current collector to form an anode electrode layer. Wherein the negative electrode active material mainly comprises graphite or carbon having a graphite-like structure, and the like. The content of these positive electrode or negative electrode active materials is not particularly limited.
Further, the functional layer of the present application is coated on the surface of the positive electrode layer and/or the surface of the negative electrode layer. In order to facilitate understanding of the structure of the diaphragm-free solid-state lithium battery provided by the application, a battery structure schematic diagram is shown in fig. 1, and the battery structure schematic diagram comprises a copper foil 1, a negative electrode layer 2, a negative electrode functional layer 3, an in-situ cured electrolyte 4, a positive electrode functional layer 5, a positive electrode layer 6 and an aluminum foil 7 which are sequentially stacked. Wherein the negative electrode functional layer 3 between the negative electrode layer 2 and the in-situ solidified electrolyte 4 may be removed, or the negative electrode functional layer 3 may remain, while the positive electrode functional layer 5 between the in-situ solidified electrolyte 4 and the positive electrode layer 6 is removed.
In an alternative embodiment of the present application, the composition of the functional layer comprises, in mass%, 70% -90% of the coating material, which may be, for example, 70%, 80%, 90% or any value between 70% -90%, and 10% -30% of the binder, which may be, for example, 10%, 20%, 30% or any value between 10% -30%; the thickness of the functional layer is 20 μm to 50 μm, and may be, for example, 20 μm, 30 μm, 40 μm, 50 μm or any value between 20 μm and 50 μm.
In an alternative embodiment of the present application, the coating material comprises a porous material or a solid electrolyte material; the binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber and cellulose.
In an alternative embodiment of the present application, the porous material comprises any one of magnesium oxide, zirconium dioxide, silicon dioxide, titanium dioxide and aluminum oxide, and the particle size of the porous material is 1 μm to 20 μm, for example, may be 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 15 μm, 20 μm or any value between 1 μm and 20 μm. The pore size of the porous material is 10nm to 100nm, and may be, for example, 10nm, 20nm, 30nm, 50nm, 75nm, 85nm, 100nm or any value between 10nm and 100nm.
The oxide is selected as the porous material, so that on one hand, the oxide has low electronic conductivity and extremely low thermal conductivity, namely electronic insulation, and can prevent the positive electrode and the negative electrode from being short-circuited, and on the other hand, the high specific surface area and the high porosity of the porous material are utilized to ensure that the lithium ion transmission channel is not influenced.
In an alternative embodiment of the present application, the solid electrolyte material comprises a perovskite type electrolyte Li 0.33 La 0.557 TiO 3 Garnet-type electrolyte Li 7 La 3 Zr 2 O 12 Fast ion conductor Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 And L i2 S-P 2 S 5 Any one of the sulfide-based electrolytes.
The solid electrolyte materials are also selected because the electrolytes are oxide or sulfide based electrolytes, which can greatly reduce the transmission of electrons, but the existence of lithium ions in the solid electrolyte does not affect the transmission of lithium ions.
In an alternative embodiment of the present application, the composition of the in situ cured electrolyte comprises, in mass percent, 5% -50% of polymerized monomer, e.g., may be anywhere between 5%, 10%, 15%, 20%, 35%, 45%, 50% or 1% -50%, 0-10% of a fast ion conductor additive, e.g., may be anywhere between 0, 1%, 2%, 3%, 5%, 8%, 10% or 0-10%, 50-95% of a solvent, e.g., may be anywhere between 50%, 60%, 70%, 80%, 90%, 95% or 50% -95%, an initiator, the mass of which is 0.05% -1%, e.g., may be anywhere between 0.05%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1% or 0.05% -1%, and a lithium salt, the concentration of which is 0.1mol/L-3mol/L, e.g., may be anywhere between 0.1/L, 0.3, 0/L/1% or 0.3/L, 0.3/mol/L, or any value of the total mass of the polymerized monomer.
In an alternative embodiment of the present application, the polymeric monomer includes at least one of methyl methacrylate, vinylene carbonate, ethyl methacrylate, methoxypolyethylene glycol acrylate, glycidyl methacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylpropane triacrylate, ethylene glycol diacrylate, ethylene carbonate, ethylene oxide, and 1, 3-dioxolane.
In an alternative embodiment of the present application, the fast ion conductor additive comprises Li 6.4 Al 0.24 La 3 Zr 2 O 12 、Li 7 La 3 Zr 2 O 12 And at least one of succinonitrile. The fast ion conductor additive is mainlyThe ionic conductivity of the electrolyte after in situ curing is further improved.
In an alternative embodiment of the present application, the solvent comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, gamma-butyrolactone, methyl formate, dimethoxymethane, and acetonitrile.
In an alternative embodiment of the present application, the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl, dicumyl peroxide, dibenzoyl peroxide, and ammonium persulfate.
In an alternative embodiment of the present application, the lithium salt includes at least one of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethylsulfonimide, lithium tetrafluoroborate, and lithium hexafluoroarsenate.
It should be noted that the ionic conductivity of the in-situ cured electrolyte prepared from the above materials is greater than 1×10 at room temperature -3 S/cm, electrochemical stability window higher than 5V.
The application also provides a preparation method of the diaphragm-free solid lithium ion battery, which comprises the following steps:
(1) Preparing the components of the functional layer into slurry, coating the slurry on the positive electrode and/or the negative electrode, and drying to obtain a positive electrode plate and/or a negative electrode plate;
(2) Mixing the components of the electrolyte in proportion to obtain a solid electrolyte precursor solution;
(3) And assembling the positive electrode plate and the negative electrode plate into a dry battery core, injecting the solid electrolyte precursor solution, and carrying out in-situ solidification to obtain the diaphragm-free solid lithium ion battery.
In an alternative embodiment of the present application, the slurry in step (1) is prepared by mixing the components of the functional layer and a slurry solvent. Wherein the slurry solvent comprises at least one of dimethylformamide, dimethylacetamide, diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran; the mass of the slurry solvent is 50% -90% of the total mass of the slurry, and may be, for example, 50%, 60%, 70%, 80%, 90% or any value between 50% -90%.
In an alternative embodiment of the present application, the temperature of the drying in step (1) is 60-110 ℃, e.g. 60 ℃, 80 ℃, 100 ℃, 110 ℃ or any value between 60-110 ℃.
When the positive electrode and the negative electrode respectively comprise a current collector and an electrode layer, the coating specifically refers to coating the slurry of the functional layer on the surface of the electrode layer of the positive electrode and/or the surface of the electrode layer of the negative electrode, and then drying and calendaring to form a positive electrode plate and/or a negative electrode plate.
After the functional layer is obtained by drying, the coating thickness of the functional layer can be selected according to the thickness of the cell design, and then the coating is rolled by a pair of rollers, or the rolling treatment is not required.
In an alternative embodiment of the present application, the dry cells injected with the solid electrolyte precursor solution are sealed and left to stand, typically for 24 hours, before in-situ curing in step (3), so that the electrolyte is fully impregnated with the material on the functional layer. And in-situ curing, heating and curing the battery after standing for 2-12 hours at the temperature of 40-80 ℃ to enable the initiator to induce the polymerization monomer to undergo thermal polymerization to form a crosslinked copolymer network, wherein the free solvent and lithium salt are fixed in the crosslinked network, and the solid electrolyte is formed in situ in the battery cell.
Embodiments of the present invention will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The present embodiment provides a solid-state lithium battery including: copper foil 1, negative electrode layer 2, in-situ cured electrolyte 4, positive electrode functional layer 5, positive electrode layer 6 and aluminum foil 7.
The preparation method comprises the following steps:
(1) Manufacturing a positive electrode plate containing a functional layer: 8.78wt% of porous silica micropowder, 3.5wt% of polyvinylidene fluoride and 87.72wt% of dimethylacetamide solvent were mixed and stirred thoroughly to obtain a slurry for a safety coating. The safe coating slurry is uniformly coated on the active material of the positive electrode roll which is coated and rolled in a coating mode, the solvent is fully dried through a baking oven at the temperature of 100 ℃, and then the rolling treatment is carried out through a roller pair machine. Wherein, the positive electrode active material adopts ternary NCM811, the negative electrode active material adopts artificial graphite, and the thickness of the functional layer is 30 micrometers.
(2) Preparing a solid electrolyte precursor solution: methyl methacrylate, glycidyl methacrylate and commercial electrolyte (Kolu ternary 811 full-electric electrolyte) are mixed according to the mass ratio of 13:7:80, and adding azodiisobutyronitrile accounting for 0.5 percent of the total mass of the methyl methacrylate and the glycidyl methacrylate, and uniformly mixing to obtain a solid electrolyte precursor solution.
(3) Preparation of a solid-state lithium ion battery: the positive electrode roll with the coating and the negative electrode roll without the coating are directly wound or laminated into a battery core, and other processes are all prepared by adopting a standard soft package battery process except for adding a diaphragm. And then placing the battery core in pit-punching aluminum plastic, baking, injecting the prepared solid electrolyte precursor solution, enabling the liquid injection process to be consistent with that of a standard soft package battery, sealing, and standing to enable the precursor solution to be completely infiltrated in the battery core. And after the infiltration is completed, heating the battery core at 70 ℃ for 12 hours to enable the precursor solution to be cured in situ, so as to obtain the soft-package solid-state lithium battery, and carrying out electrochemical and safety tests.
Example 2
The present embodiment provides a solid-state lithium battery including: copper foil 1, negative electrode layer 2, negative electrode functional layer 3, in-situ cured electrolyte 4, positive electrode layer 6 and aluminum foil 7.
The preparation method comprises the following steps:
(1) Manufacturing a negative electrode plate containing a functional layer: 10.5 weight percent of silica porous micro powder, 4.5 weight percent of polyvinylidene fluoride and 85 weight percent of dimethylacetamide solvent are mixed and fully stirred to obtain slurry of the safety coating. The safe coating slurry is uniformly coated on the active material of the rolled negative electrode roll in a coating mode, the solvent is fully dried through a baking oven at 100 ℃, and then the roll is rolled by a roll pair machine. Wherein, the positive electrode active material adopts ternary NCM811, the negative electrode active material adopts artificial graphite, and the thickness of the functional layer is 30 micrometers.
(2) Preparing a solid electrolyte precursor solution: methyl methacrylate, glycidyl methacrylate and commercial electrolyte (Kolu ternary 811 full-electric electrolyte) are mixed according to the mass ratio of 13:7:80, adding succinonitrile accounting for 5 percent of the total mass of the solution, adding azodiisobutyronitrile accounting for 0.5 percent of the total mass of methyl methacrylate and glycidyl methacrylate, and uniformly mixing to obtain the solid electrolyte precursor solution.
(3) Preparation of a solid-state lithium ion battery: the cathode roll with the coating and the anode roll without the coating are directly wound or laminated into a battery core, and other processes are all prepared by adopting a standard soft package battery process except for adding a diaphragm. And then placing the battery core in pit-punching aluminum plastic, baking, injecting the prepared solid electrolyte precursor solution, enabling the liquid injection process to be consistent with that of a standard soft package battery, sealing, and standing to enable the precursor solution to be completely infiltrated in the battery core. And after the infiltration is completed, heating the battery core at 70 ℃ for 12 hours to enable the precursor solution to be cured in situ, so as to obtain the soft-package solid-state lithium battery, and carrying out electrochemical and safety tests.
Example 3
The present embodiment provides a solid-state lithium battery including: copper foil 1, negative electrode layer 2, negative electrode functional layer 3, in-situ cured electrolyte 4, positive electrode functional layer 5, positive electrode layer 6 and aluminum foil 7.
The preparation method comprises the following steps:
(1) Manufacturing positive and negative pole pieces containing functional layers: 18wt% of Li 6.4 Al 0.24 La 3 Zr 2 O 12 Mixing the micro powder, 2wt% of polyvinylidene fluoride and 80wt% of dimethylacetamide solvent, and fully stirring to obtainTo the slurry of the security coating. The safe coating slurry is uniformly coated on the active material of the positive and negative electrode rolls which are coated and rolled in a coating mode, the solvent is fully dried through a baking oven at 100 ℃, and then the roll treatment is carried out through a roll pair machine. Wherein, the positive electrode active material adopts ternary NCM811, the negative electrode active material adopts artificial graphite, and the thickness of the functional layer is 30 micrometers.
(2) Preparing a solid electrolyte precursor solution: methyl methacrylate, glycidyl methacrylate and commercial electrolyte (Kolu ternary 811 full-electric electrolyte) are mixed according to the mass ratio of 13:7:80, and adding azodiisobutyronitrile accounting for 0.5 percent of the total mass of the methyl methacrylate and the glycidyl methacrylate, and uniformly mixing to obtain a solid electrolyte precursor solution.
(3) Preparation of a solid-state lithium ion battery: the anode and cathode coils with the coating are directly wound or laminated into the battery core, and other processes are prepared by adopting a standard soft package battery process except for adding a diaphragm. And then placing the battery core in pit-punching aluminum plastic, baking, injecting the prepared solid electrolyte precursor solution, enabling the liquid injection process to be consistent with that of a standard soft package battery, sealing, and standing to enable the precursor solution to be completely infiltrated in the battery core. And after the infiltration is completed, heating the battery core at 70 ℃ for 12 hours to enable the precursor solution to be cured in situ, so as to obtain the soft-package solid-state lithium battery, and carrying out electrochemical and safety tests.
Example 4
The difference is that the thickness of the functional layer is 50 μm as in example 3.
Comparative example 1
The comparative example provides a conventional liquid lithium battery, the dry battery is prepared by a standard soft package battery process, wherein the anode and cathode plates are respectively uncoated anode and cathode rolls, the electrolyte is commercial electrolyte (three-element 811 full-electric electrolyte of Korea) and the diaphragm is commercial double-sided Al 2 O 3 The ceramic coats the separator. After the lamination of the battery cell is completed, adding a diaphragm, placing the battery cell in a pit punching aluminum plastic, baking, injecting commercial electrolyte, sealing, and standing to completely infiltrate the electrolyte into the battery cell. After the infiltration is completed, electricity is usedThe core was heated at 70 ℃ for 12 hours to obtain a standard soft-pack liquid lithium battery, and electrochemical and safety tests were performed.
Comparative example 2
The comparative example provides a liquid lithium battery with positive and negative electrode functional layers and no diaphragm, wherein the thickness of the functional layers of the positive and negative electrode pole pieces is 50 micrometers respectively, the specific preparation method is the same as that of the example 3, commercial liquid electrolyte (three elements 811 full-electric electrolyte of Ke Lou) is injected after the lamination of the battery core is finished, and the battery core is kept stand after being sealed, so that the electrolyte is completely immersed in the battery core. After the infiltration is completed, the battery cell is heated for 12 hours at 70 ℃ to obtain a soft-package liquid lithium battery, and electrochemical and safety tests are carried out.
Comparative example 3
The comparative example provides an in-situ cured solid-state lithium battery without a functional layer and with a diaphragm, the preparation method of a dry cell is identical to that of comparative example 1, after the lamination of the cell is completed, the diaphragm is added to prepare the same solid electrolyte precursor solution as in example 3, the subsequent in-situ curing process is also identical to that of example 3, and the soft-package solid-state lithium battery is obtained and subjected to electrochemical and safety tests.
The batteries prepared in examples 1 to 4 and comparative examples 1 to 3 described above had a design capacity of 2Ah, and the specific test results are shown in table 1 below.
TABLE 1 discharge Performance and safety test results for batteries of examples 1-3 and comparative examples 1-3
As can be seen from the test results in table 1, the first effect and the energy density of the batteries of examples 1 to 4 were slightly lower than those of the comparative document 1, but the attenuation was smaller, wherein the first effect and the energy density of example 4 were relatively lower because the functional layer was thicker and the impedance was large. Whereas, the results of examples 1-4 were better than those of comparative example 1 in terms of the needling results.
In addition, the first effect of the non-diaphragm liquid battery assembled by the coating material in comparative example 2 is lower, which indicates that the non-diaphragm liquid battery in comparative example 2 can be charged and discharged normally, but the efficiency is lower, and the micro-short circuit may occur in the battery cell. In contrast, comparing the needling results of comparative examples 1 and 3, it is apparent that the safety of the battery can be improved to some extent after the electrolyte in the battery is cured.
In summary, the application combines the anode and cathode functional coatings with the in-situ curing scheme to obtain the diaphragm-free solid lithium ion battery, and the safety of the battery can be greatly improved while the normal electrochemical performance of the battery is ensured.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (15)

1. A separator-less solid state lithium ion battery comprising: a positive electrode, a negative electrode, an in-situ cured electrolyte, and a functional layer, the electrolyte being located between the positive electrode and the negative electrode;
the functional layer is located between the positive electrode and the electrolyte, and/or the functional layer is located between the negative electrode and the electrolyte;
the functional layer comprises a coating material with an electronic insulation function;
the coating material is a porous material;
the porous material includes any one of magnesia, zirconia, silica, titania and alumina.
2. The separator-free solid state lithium ion battery of claim 1, wherein the composition of the functional layer comprises 70% -90% of the coating material and 10% -30% of the binder in mass percent, and the functional layer has a thickness of 20 μm-50 μm;
the binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber and cellulose.
3. The separator-free solid state lithium ion battery of claim 2, wherein the porous material has a particle size of 1 μm to 20 μm and a pore size of 10nm to 100nm.
4. The separator-free solid state lithium ion battery of claim 1, wherein the electrolyte comprises, in mass percent, 5% -50% polymerized monomer, 0-10% fast ion conductor additive, 50-95% solvent, initiator, and lithium salt;
the mass of the initiator is 0.05% -1% of the total mass of the polymerization monomers;
the concentration of the lithium salt in the polymerization precursor solution formed by mixing the polymerization monomer, the fast ion conductor additive, the initiator and the solvent is 0.1mol/L to 3mol/L.
5. The separator-free solid state lithium ion battery of claim 4, wherein the polymeric monomer comprises at least one of methyl methacrylate, vinylene carbonate, ethyl methacrylate, methoxypolyethylene glycol acrylate, glycidyl methacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylpropane triacrylate, ethylene glycol diacrylate, ethylene carbonate, ethylene oxide, and 1, 3-dioxolane.
6. The separator-free solid state lithium ion battery of claim 4 wherein the fast ion conductor additive comprises Li 6.4 Al 0.24 La 3 Zr 2 O 12 、Li 7 La 3 Zr 2 O 12 And at least one of succinonitrile.
7. The separator-free solid state lithium ion battery of claim 4, wherein the solvent comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, gamma-butyrolactone, methyl formate, dimethoxymethane, and acetonitrile.
8. The separator-free solid state lithium ion battery of claim 4, wherein the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl, dicumyl peroxide, dibenzoyl peroxide, and ammonium persulfate.
9. The separator-free solid state lithium ion battery of claim 4, wherein the lithium salt comprises at least one of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethylsulfonimide, lithium tetrafluoroborate, and lithium hexafluoroarsenate.
10. The separator-free solid state lithium ion battery of any of claims 1-9, wherein the positive electrode and the negative electrode comprise a current collector and an electrode layer, respectively;
the functional layer is located between the electrode layer and the electrolyte.
11. A method of making a separator-free solid state lithium ion battery according to any one of claims 1-10, comprising: preparing the raw materials of the functional layer into slurry, and coating the slurry on the positive electrode and/or the negative electrode to obtain a positive electrode plate and/or a negative electrode plate;
mixing the raw materials of the electrolyte to obtain a solid electrolyte precursor solution;
and assembling the positive electrode plate and the negative electrode plate into a dry battery core, injecting the solid electrolyte precursor solution, and carrying out in-situ solidification to obtain the diaphragm-free solid lithium ion battery.
12. The method for preparing a diaphragm-free solid state lithium ion battery according to claim 11, wherein the slurry is prepared by mixing a coating material of the functional layer, a binder and a slurry solvent;
the slurry solvent comprises at least one of dimethylformamide, dimethylacetamide, diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran;
the mass of the slurry solvent accounts for 50% -90% of the total mass of the slurry.
13. The method of claim 12, wherein after said coating, a drying process is further performed, said drying temperature being 60 ℃ to 110 ℃.
14. The method for preparing a separator-free solid-state lithium ion battery according to claim 12, wherein when the positive electrode and the negative electrode respectively comprise a current collector and an electrode layer, the coating means coating the slurry on the surface of the electrode layer of the positive electrode and/or the surface of the electrode layer of the negative electrode.
15. The method of any one of claims 11-14, wherein the dry cells injected with the solid electrolyte precursor solution are sealed and allowed to stand prior to the in-situ curing;
and in the in-situ curing, heating and curing the battery after standing at the temperature of 45-80 ℃ for 2-12 h.
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