CN116093253A - Battery pole piece, preparation method thereof and semi-solid lithium ion battery - Google Patents
Battery pole piece, preparation method thereof and semi-solid lithium ion battery Download PDFInfo
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- CN116093253A CN116093253A CN202310384245.8A CN202310384245A CN116093253A CN 116093253 A CN116093253 A CN 116093253A CN 202310384245 A CN202310384245 A CN 202310384245A CN 116093253 A CN116093253 A CN 116093253A
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- 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
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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
- 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
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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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
- 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
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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
- 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
- H01M4/624—Electric conductive fillers
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Abstract
The application provides a battery pole piece, a preparation method thereof and a semisolid lithium ion battery, and relates to the technical field of lithium ion batteries. The battery pole piece comprises a current collector, an active material layer, an electronic insulating functional layer and a polymer electrolyte; the active material layer is located between the current collector and the electronic insulating functional layer, and the polymer electrolyte is filled in pores of the active material layer and the electronic insulating functional layer. The preparation method of the battery pole piece comprises the following steps: coating slurry containing raw materials of an electronic insulating functional layer on a first pole piece containing an active material layer to obtain a second pole piece; and soaking the second pole piece in the polymer electrolyte precursor solution, taking out, and then carrying out in-situ curing to obtain the battery pole piece. The semi-solid battery comprises the battery pole piece. The semi-solid lithium ion battery has excellent electrochemical performance and simultaneously can maintain excellent safety performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a battery pole piece, a preparation method thereof and a semisolid lithium ion battery.
Background
The key of the development of the modern energy field is a novel power system taking new energy sources such as solar energy, wind energy, water and electricity as main bodies, however, a lithium ion battery with high energy density, high power density, high safety and long service life is the key of the efficient application of the new energy source green electric energy. The commercial lithium ion battery widely used at present is mainly based on liquid electrolyte, and is easy to decompose a solid electrolyte layer (SEI) at a lower temperature, a series of thermal runaway behaviors such as diaphragm melting, electrode decomposition heat release, electrolyte combustion and the like are triggered, the risk of fire explosion exists, and safety accidents are caused. Meanwhile, in the development process of pursuing higher specific energy lithium ion batteries, in order to further increase the energy density of the batteries, high-capacity negative electrodes (such as silicon and metallic lithium negative electrodes) and positive electrode materials (high-nickel positive electrode materials) are used to replace commonly used negative electrode materials graphite and conventional positive electrode materials (such as LiCoO) 2 And LiFePO 4 ) This further worsens the safety problem of lithium ion batteries, increases the potential safety hazard of batteries, and seriously hinders the further application of lithium ion batteries. Therefore, improving the safety and energy density of lithium ion batteries is two important and urgent tasks in the field of lithium batteries.
The thermal safety and the needling pass rate of the battery are important indexes for evaluating the safety of the lithium ion battery. In the prior art, the safety of the battery can be improved to a certain extent by the technical schemes of electrode active material modification, flame-retardant electrolyte additive, high-temperature resistant diaphragm, in-situ curing, functional coating and the like. The in-situ curing technology and the functional coating technology can respectively and greatly improve the thermal safety and the needling passing rate of the battery, but can cause certain loss to the electrochemical performance, particularly the rate capability and the energy density of the lithium ion battery. The simple combination of the in-situ curing technology and the functional coating technology can not improve the thermal safety and the needling pass rate of the lithium battery at the same time, but can greatly damage the electrical performance of the battery. Therefore, there is a need to develop a comprehensive strategy that combines the in-situ curing technology and the functional coating technology organically, while maintaining or even improving the electrochemical performance of the lithium ion battery, and at the same time improving the thermal safety and the needling pass rate of the battery.
Disclosure of Invention
The purpose of the application is to provide a battery pole piece, a preparation method thereof and a semisolid lithium ion battery, so that the safety and electrochemical performance of the lithium ion battery are improved.
In order to achieve the above object, the technical scheme of the present application is as follows:
a battery pole piece comprises a current collector, an active material layer, an electronic insulating functional layer and a polymer electrolyte;
the active material layer is located between the current collector and the electronic insulating functional layer, and the polymer electrolyte is filled in pores of the active material layer and the electronic insulating functional layer.
In a preferred embodiment, the battery pole piece meets at least one of the following conditions:
a. the thickness of the electronic insulating functional layer is 1-20 mu m;
b. the electronic insulating functional layer comprises 70-95% of inorganic material and 5-30% of binder by mass percent;
c. the polymer electrolyte is obtained by in-situ polymerization of a polymer electrolyte precursor solution.
Optionally, the battery pole piece satisfies at least one of the following conditions:
d. the inorganic material comprises a porous oxide material or an inorganic solid electrolyte material;
e. the binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber and cellulose;
f. the polymer electrolyte precursor solution includes: a polymerization monomer, lithium salt, an organic solvent and an initiator.
Further preferably, at least one of the following conditions is also satisfied:
g. the porous oxide material comprises at least one of magnesium oxide, zirconium dioxide, silicon dioxide, titanium dioxide and aluminum oxide;
h. the average particle diameter of the porous oxide material is 1-20 mu m;
i. the average pore diameter of the porous oxide material is 10nm-100nm;
j. the inorganic solid electrolyte material comprises at least one of a NASICON structure material, a garnet structure material and a perovskite structure material;
k. the NASICON structural material comprises Li 1+x Al x Ge 2-x (PO 4 ) 3 、Li 1+y Al y Ti 2-y (PO 4 ) 3 Based on Li 1+ x Al x Ge 2-x (PO 4 ) 3 Is based on Li 1+y Al y Ti 2-y (PO 4 ) 3 Wherein 0.ltoreq.x.ltoreq. 0.75,0.ltoreq.y.ltoreq.0.5;
the garnet structure material comprises Li 7-a La 3 Zr 2-a O 12 And based on Li 7-a La 3 Zr 2-a O 12 Wherein 0.ltoreq.a.ltoreq.1;
m. the perovskite structure material comprises Li 3b La 2/3-b TiO 3 And based on Li 3b La 2/3-b TiO 3 At least one of the dopants of (2)Wherein b is more than or equal to 0.06 and less than or equal to 0.14;
the polymerization monomer comprises at least one of methyl methacrylate, ethylene carbonate, ethyl methacrylate, methoxy polyethylene glycol acrylate, glycidyl methacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylpropane triacrylate, polyethylene glycol diacrylate, ethylene carbonate, ethylene oxide and 1, 3-dioxolane;
the lithium salt comprises at least one of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonyl imide, lithium tetrafluoroborate and lithium hexafluoroarsenate;
the organic solvent comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, dimethoxymethane, gamma-butyrolactone and acetonitrile;
the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl, dicumyl peroxide, dibenzoyl peroxide and ammonium persulfate.
In a preferred embodiment, when the battery electrode sheet is a positive electrode sheet, the raw material of the active material layer includes a positive electrode active material including LiCoO 2 、LiNiO 2 、LiMnO 2 、LiNi p Co 1-p O 2 、LiNi p Co q Mn 1-p-q O 2 、LiNi p Co q Al 1-p-q O 2 Wherein 0.5.ltoreq.p < 1,0 < q < 0.5, and p+q=1;
when the battery pole piece is a negative pole piece, the raw material of the negative active material layer comprises a negative active material, and the negative active material comprises at least one of artificial graphite, natural graphite and silicon carbon negative electrode material.
The application also provides a preparation method of the battery pole piece, which comprises the following steps: coating slurry containing the active material layer raw material on at least one surface of the current collector to obtain a first pole piece;
coating the slurry containing the raw materials of the electronic insulating functional layer on the active material layer of the first pole piece to obtain a second pole piece;
and immersing the second electrode plate in the polymer electrolyte precursor solution, taking out, and then carrying out in-situ solidification to obtain the battery electrode plate.
In a preferred embodiment, the preparation method fulfils at least one of the following conditions:
the slurry containing the raw materials of the electronic insulating functional layer comprises an inorganic material, a binder and a slurry solvent, wherein the slurry solvent comprises at least one of dimethylformamide, dimethylacetamide, diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran;
s. before the in-situ curing, the method further comprises: removing excess polymer electrolyte precursor solution from the second electrode sheet surface;
and t, triggering the in-situ curing by adopting any one of heat, light and radiation.
Further preferably, the mass ratio of the inorganic material, the binder and the slurry solvent is (8-9.5): (0.5-3.5): (60-95).
The application also provides a semi-solid lithium ion battery, which comprises a positive plate and a negative plate;
the positive electrode plate and/or the negative electrode plate adopt the battery electrode plate.
In a preferred embodiment, the semi-solid lithium ion battery further comprises a separator and an electrolyte, the separator and the electrolyte being located between the positive electrode sheet and the negative electrode sheet.
The beneficial effects of this application:
this application has set up electronic insulation functional layer on the battery pole piece, and this electronic insulation functional layer has good mechanical properties, structural stability and heat stability, has good electron separation effect simultaneously, can improve the internal resistance when the battery acupuncture, reduces the heat production in the acupuncture process, improves the battery acupuncture rate of passing through. In addition, the electronic insulating functional layer can also prevent the positive electrode and the negative electrode from being in direct contact short circuit at high temperature, slow down or even avoid the occurrence of thermal runaway, and improve the thermal safety of the battery. According to the battery pole piece, the polymer electrolyte and the electronic insulating functional coating are organically combined, so that the construction of a uniform and rapid lithium ion passage inside the battery pole piece is ensured, and the thermal safety and the needling passing rate of the battery are greatly improved while excellent electrochemical performance is maintained.
Further, the main components of the polymer electrolyte consist of linear polymer chain segments and cross-linked polymer chain segments, so that the polymer electrolyte has certain ductility and rebound resilience, and the volume change of the pole piece in the charging and discharging process can be self-adapted by filling the pores of the pole piece; when the electrode material expands, the porosity of the electrode plate is reduced, the electrolyte is extruded out of the electrode plate, after the volume of the electrode material is retracted, the electrolyte can rebound into the pore channel rapidly along with the electrode plate when the porosity of the electrode plate is recovered, so that non-uniform reflux and partial lean solution which possibly occur when liquid electrolyte is used are avoided, the battery is prevented from generating unpredictable circulating water jump, and the circulating stability and reliability of the battery are improved.
According to the preparation method of the battery pole piece, the precursor solution of the polymer electrolyte is poured into the pores of the active material layer and the electronic insulating functional layer by using a soaking method, the polymerization monomer in the precursor solution is in atomic level contact with the electrode active material in the battery pole piece, then in-situ solidification is carried out, and the solidified polymerization monomer is converted into the polymer electrolyte, so that the atomic level good contact between the electrode active material and the polymer electrolyte is realized. By introducing the polymer electrolyte through an in-situ curing method, the interface impedance inside the battery pole piece is reduced, and the electrochemical performance of the anode and/or the cathode is improved. The manufacturing process of the battery pole piece has high compliance with the manufacturing process of the battery pole piece in the traditional lithium ion battery, has high product line compatibility, can effectively control the upgrade cost of the product line, and is suitable for large-scale popularization.
In the semisolid lithium ion battery, the battery pole piece with the electronic insulating functional coating and the polymer electrolyte is assembled into the battery, so that the precursor solution solidified in situ can be fully and uniformly soaked in the battery pole piece, and a smooth lithium ion channel is constructed. Furthermore, when the semi-solid lithium ion battery is assembled, only a small amount of electrolyte is injected to wet the diaphragm, so that the content of the electrolyte in the battery is greatly reduced, the energy density is improved, the content of combustible polymer in the electrolyte is reduced, and the safety performance of the battery is further improved.
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 view of the structure of a battery pole piece of the present application;
fig. 2 is a first cycle charge-discharge plot of the semi-solid lithium ion battery of example 1;
fig. 3 is a graph showing the cycle stability of the semi-solid lithium ion battery of example 1.
Illustration of:
1-a current collector; 2-electrode active material; 3-a binder; 4-conductive agent; a 5-polymer electrolyte; 6-an electronic insulating functional layer.
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.
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 battery pole piece, which comprises a current collector, an active material layer, an electronic insulation functional layer and a polymer electrolyte. Wherein the active material layer is positioned between the current collector and the electronic insulating functional layer, and the polymer electrolyte is filled in the pores of the active material layer and the electronic insulating functional layer.
The raw materials of the active material layer generally include an electrode active material, a conductive agent and an electrode binder, wherein the conductive agent and the electrode binder can be selected from conductive agents and electrode binder materials commonly used in the anode and the cathode of the lithium ion battery, and the materials are not particularly limited herein; the electrode active material is selected according to whether the battery pole piece is a positive pole piece or a negative pole piece.
In an alternative mode of the present application, if the battery pole piece is a positive pole piece, the electrode active material is a positive active material, and the positive active material includes LiCoO 2 、LiNiO 2 、LiMnO 2 、LiNi p Co 1-p O 2 、LiNi p Co q Mn 1-p- q O 2 、LiNi p Co q Al 1-p-q O 2 Wherein 0.5.ltoreq.p < 1,0 < q < 0.5, and p+q=1.
And if the battery pole piece is a negative pole piece, the electrode active material is a negative pole active material, wherein the negative pole active material comprises at least one of artificial graphite, natural graphite and silicon carbon negative pole material.
Fig. 1 shows a schematic structure of a battery pole piece comprising an electronically insulating functional layer and a polymer electrolyte. Wherein, the electrode active material 2, the binder 3 and the conductive agent 4 on the surface of the current collector 1 form an active material layer of the battery pole piece, and the active material layer is positioned between the current collector 1 and the electronic insulation functional layer 6; the polymer electrolyte 5 is present between the active material layer and the pores of the electronically insulating functional layer 6.
In an alternative form of the present application, the thickness of the electronically insulating functional layer is 1 μm to 20 μm, and may be, for example, 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm or any value between 1 μm and 20 μm.
In an alternative manner of the present application, the electronic insulating functional layer may include 70% -95% of inorganic material and 5% -30% of binder by mass percentage, for example, 80% of inorganic material and 20% of binder, 90% of inorganic material and 10% of binder, 95% of inorganic material and 5% of binder, etc., which are not particularly limited herein.
In a preferred mode of the present application, the inorganic material comprises a porous oxide material or an inorganic solid electrolyte material. Wherein, the porous oxide material has the characteristics of high porosity, low thermal conductivity and low electron conductivity; the inorganic solid electrolyte material has the characteristics of high ion conductivity and low electron conductivity.
Further preferably, the porous oxide material comprises at least one of magnesium oxide, zirconium dioxide, silicon dioxide, titanium dioxide and aluminum oxide.
Further preferably, the porous oxide material has an average particle diameter of 1 μm to 20 μm, for example, may be 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm or any value between 1 μm and 20 μm; the porous oxide material has an average pore size of 10nm to 100nm, and may be, for example, 10nm, 20nm, 50nm, 80nm, 100nm or any value between 10nm and 100 nm.
Further preferably, the inorganic solid electrolyte material includes at least one of NASICON structural material, garnet structural material, perovskite structural material. The average particle diameter of the particles of these inorganic solid electrolyte materials is 1 μm to 20 μm.
Wherein the NASICON structural material comprises Li 1+x Al x Ge 2-x (PO 4 ) 3 、Li 1+y Al y Ti 2-y (PO 4 ) 3 Based on Li 1+ x Al x Ge 2-x (PO 4 ) 3 Is based on Li 1+y Al y Ti 2-y (PO 4 ) 3 Wherein 0.ltoreq.x.ltoreq.0.75, may be, for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or any value between 0 and 0.75, 0.ltoreq.y.ltoreq.0.5, may be, for example, 0, 0.1, 0.2, 0.3, 0.4 or any value between 0 and 0.5.
Garnet structural material comprising Li 7-a La 3 Zr 2-a O 12 And based on Li 7-a La 3 Zr 2-a O 12 Wherein 0.ltoreq.a.ltoreq.1, may be, for example, 0, 0.25, 0.5, 0.75, 1 or any value between 0 and 1.
The perovskite structure material comprises Li 3b La 2/3-b TiO 3 And based on Li 3b La 2/3-b TiO 3 Wherein 0.06.ltoreq.b.ltoreq.0.14, e.g. may be 0.06, 0.08, 0.1, 0.12, 0.14 or any value between 0.06 and 0.14.
It should be noted that these dopants are mainly solid electrolyte materials doped with doping elements, wherein the doping elements include at least one element of Ta, nb, sb, sr, te.
In a preferred form of the present application, the binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber, and cellulose.
It should be noted that the thickness of the electronic insulating functional coating, the particle size of the inorganic material, the pore diameter of the inside, and the like in the battery pole piece of the present application all need to be specially set. If the thickness of the electronic insulating functional coating is too thick, the particle size and the pore diameter of the inorganic particles are too small, the coating density is high, and when the battery pole piece is used in a battery, the needling passing rate of the battery is high, but the penetration rate can influence the electrolyte in the battery, and further influence the electrical property of the finally manufactured lithium ion battery; if the electronic insulating functional coating is too thin, the particle size and the pore diameter of the inorganic particles are large, the coating density is low, and the internal resistance is small and the needling passing rate is low although the electric performance of the battery is less affected.
In an alternative form of the present application, the polymer electrolyte is a polymer electrolyte precursor solution obtained by in situ polymerization.
In a preferred mode of the present application, the polymer electrolyte precursor solution includes: a polymerization monomer, lithium salt, an organic solvent and an initiator.
Further preferably, the polymeric monomer includes at least one of methyl methacrylate, ethylene carbonate, ethyl methacrylate, methoxypolyethylene glycol acrylate, glycidyl methacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylpropane triacrylate, polyethylene glycol diacrylate, ethylene carbonate, ethylene oxide, and 1, 3-dioxolane.
Further preferably, the lithium salt includes at least one of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethylsulfonimide, lithium bistrifluorosulfonylimide, lithium tetrafluoroborate and lithium hexafluoroarsenate;
further preferably, the organic solvent includes at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methyl formate, dimethoxymethane, γ -butyrolactone, and acetonitrile;
further preferably, the initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl, dicumyl peroxide, dibenzoyl peroxide and ammonium persulfate.
The application also provides a preparation method of the battery pole piece, which comprises the following steps:
s1, coating slurry containing active material layer raw materials on at least one surface of a current collector to prepare an active material layer, and further obtaining a first pole piece;
s2, coating slurry containing raw materials of an electronic insulating functional layer on an active material layer of the first pole piece to prepare an electronic insulating functional layer, and further obtaining a second pole piece;
s3, soaking the second pole piece in the polymer electrolyte precursor solution, taking out, and then carrying out in-situ solidification to obtain the battery pole piece.
Wherein, the slurry containing the active material layer raw material in S1 includes: an electrode active material, a conductive agent, an electrode binder, and a solvent. In preparing the positive electrode active material layer, a low molecular weight, volatile solvent such as N-methylpyrrolidone (NMP), methanol, ethanol, or the like can be generally selected; in preparing the anode active material layer, deionized water or the like may be used as the solvent. After the current collector is coated, drying and rolling treatment are needed, and the specific preparation process is the same as that of electrode rolls in traditional lithium ion batteries in industry.
In an alternative mode of the present application, the slurry containing the raw material of the electronic insulating functional layer in S2 includes an inorganic material, a binder, and a slurry solvent. Wherein, the inorganic material and the binder are the preferable materials in the battery pole piece; the slurry solvent comprises at least one of dimethylformamide, dimethylacetamide, diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.
Preferably, the mass ratio of the inorganic material, the binder and the slurry solvent is (8-9.5): (0.5-3.5): (60-95), for example, may be 8:2: 90. 8.5:1.5: 70. 8.78:3.5:87.72, 9:1: 80. 9.5:0.5:60 or (8-9.5): (0.5-3.5): (60-95).
Further, after the application of the slurry containing the electronic insulating functional layer raw material is completed, it is necessary to perform a drying treatment to volatilize the slurry solvent therein. After the drying is completed, rolling may or may not be performed.
In an alternative manner of the present application, S3 further includes, before performing in-situ curing: and removing excess polymer electrolyte precursor solution on the surface of the second electrode plate.
In an alternative form of the present application, the in situ curing in S3 is triggered by any one of heat, light, and radiation.
Specifically, after the polymer electrolyte precursor solution is ensured to fully infiltrate pores of each layer in the pole piece, the pole piece is taken out from the precursor solution, superfluous precursor solution on the surface is wiped off, and in-situ solidification is triggered by means of heat/light/radiation and the like, so that the battery pole piece is obtained.
The application also provides a semi-solid lithium ion battery, which comprises a positive plate and a negative plate. The positive electrode plate can be the battery electrode plate, and the negative electrode plate is a plate with a negative electrode active material layer only arranged on a negative electrode current collector; or the positive plate uses a plate with only a positive active material layer on the positive current collector, and the negative plate uses the battery plate; or both the positive plate and the negative plate use the battery plate.
In one alternative of the present application, the semi-solid lithium ion battery further comprises a separator and an electrolyte. Wherein, diaphragm and electrolyte are located between positive plate and the negative plate. The diaphragm mainly plays a role of blocking electrons and allowing lithium ions to pass through; the electrolyte mainly plays a role of wetting the diaphragm and ensuring the circulation of lithium ions between the positive plate and the negative plate.
In the charging process of the conventional common liquid lithium ion battery (comprising a cathode with high silicon content), electrolyte in a pore of the cathode can be extruded out due to the expansion of the silicon volume, so that an ion passage in the cathode pole piece is blocked, the circulation stability is poor, and the circulation water jump is easy to cause. In the semi-solid battery, when the silicon-carbon anode material with high silicon content is selected to be used in the anode plate of the battery, and the electronic insulation functional layer and the polymer electrolyte are arranged on the anode plate, the polymer electrolyte is contained in the pores of the anode plate, and has higher viscosity, so that the stability of an ion passage can be ensured in the volume expansion process of the silicon-carbon anode, and the cycle stability of the lithium ion battery is improved.
When the semi-solid lithium ion battery is prepared, the positive electrode piece, the negative electrode piece and the diaphragm can be prepared into a dry battery core through the same process of lamination or winding of the traditional lithium battery, the dry battery core is packaged in an aluminum plastic film, a small amount of electrolyte is injected, and the semi-solid lithium ion battery is obtained after full infiltration.
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 embodiment provides a battery pole piece, which comprises a positive pole piece and a negative pole piece, and the specific preparation method comprises the following steps:
(1) And respectively and uniformly mixing the positive and negative active substances with a binder, a conductive agent and a solvent to prepare positive electrode slurry and negative electrode slurry, and correspondingly and uniformly coating the positive electrode slurry and the negative electrode slurry on the positive electrode current collector and the negative electrode current collector to obtain an active substance layer, drying and rolling to obtain a positive electrode roll and a negative electrode roll. Wherein, the specific pole coil preparation process is the same as the traditional pole coil preparation process of the lithium ion battery in the industry, and the positive electrode active material adopts ternary NCM811 (LiNi 0.83 Co 0.11 Mn 0.06 ) The negative electrode active material adopts a silicon-carbon negative electrode material.
(2) Porous silica micropowder, polyvinylidene fluoride and dimethylacetamide solvent according to the following ratio of 8: and 2, uniformly mixing the materials according to the mass ratio of 90 to obtain slurry for preparing the electronic insulating functional layer, uniformly coating the slurry on the active material layers of the rolled positive electrode roll and the rolled negative electrode roll respectively in a coating mode, placing the active material layers in a baking oven at 110 ℃, fully drying the slurry solvent, and carrying out rolling treatment on the slurry solvent by a roller to obtain the electronic insulating functional layer with the thickness of 20 microns.
(3) Methyl methacrylate, polyethylene glycol diacrylate and lithium hexafluorophosphate are added into an organic solvent (ethylene carbonate and diethyl carbonate, 3:7vol%) and mixed uniformly, and azodiisobutyronitrile is added and mixed uniformly, wherein the mass of the azodiisobutyronitrile is 0.5% of the total mass of the methyl methacrylate and the polyethylene glycol diacrylate, so that a polymer electrolyte precursor solution is obtained.
(4) Soaking the anode coil and the cathode coil with the electronic insulating functional layer prepared in the step (2) in the polymer electrolyte precursor solution prepared in the step (3) for 12 hours, taking out and wiping off redundant liquid drops on the surface of the electrode plate after full soaking, putting the soaked electrode coil into a sealing bag, and heating at 60 ℃ for 12 hours to enable the polymer electrolyte precursor solution to be cured in situ, so as to obtain the anode plate and the cathode plate.
The embodiment also provides a semi-solid lithium ion battery, and the specific preparation method comprises the following steps:
the positive and negative electrode plates prepared in the embodiment are manufactured into an electric core through a lamination process, the lamination process is the same as the traditional standard soft package battery preparation method, and the diaphragm adopts a PP diaphragm. And then placing the prepared battery core in a pit-punching aluminum-plastic film, baking, injecting a small amount of silicon-carbon electrolyte, keeping the injection process consistent with that of a standard soft-package battery, sealing, and standing to enable a diaphragm in the battery core to be completely infiltrated with the electrolyte, thereby obtaining the semi-solid lithium ion battery.
Example 2
The difference from example 1 is that: in step (2) of the method for producing a battery electrode sheet of this example, LATP (Li having a particle diameter of 1 μm) was selected 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Materials, polyvinylidene fluoride and dimethylacetamide solvents according to 8:2:90 mass ratio and evenly mixing.
Example 3
The difference from example 1 is that: in step (2) of the method for preparing a battery pole piece of this embodiment, LLZTO (Li with a particle size of 1 μm is selected 6.5 La 3 Zr 1 .4 Ta 0.6 O 12 ) Materials, polyvinylidene fluoride and dimethylacetamide solvents according to 8:2:90 mass ratio and evenly mixing.
Example 4
The difference from example 1 is that: in step (2) of the method for producing a battery electrode sheet of this example, LLTO (Li having a particle diameter of 1 μm) was selected 0.3 La 0.57 TiO 3 ) Materials, polyvinylidene fluoride and dimethylacetamide solvents according to 8:2:90 mass ratio and evenly mixing.
Example 5
The difference from example 1 is that: the mass ratio of the porous silica micropowder, polyvinylidene fluoride and dimethylacetamide solvent in the step (2) of the preparation method of the battery pole piece is 8.78:3.5:87.72; meanwhile, the pentaerythritol tetraacrylate is selected to replace methyl methacrylate and polyethylene glycol diacrylate in the step (3).
Example 6
The difference from example 5 is that: in the step (3) of the preparation method of the battery pole piece of the embodiment, ethylene carbonate is selected to be used as a polymerization monomer, and lithium bis (fluorosulfonyl) imide is used as a lithium salt to replace pentaerythritol tetraacrylate and lithium hexafluorophosphate in the embodiment 5.
Example 7
The difference from example 5 is that: in the step (2) of the preparation method of the battery pole piece, the mass ratio is 8.78:3.5: LATP of 87.72 (Li having a particle diameter of 1 μm) 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Materials, polyvinylidene fluoride and dimethylacetamide solvents.
Example 8
The difference from example 6 is that: in the step (2) of the preparation method of the battery pole piece, the mass ratio is 8.78:3.5: LATP of 87.72 (Li having a particle diameter of 1 μm) 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Materials, polyvinylidene fluoride and dimethylacetamide solvents.
Example 9
The battery pole piece of this embodiment only comprises a positive pole piece, and the preparation method is the same as that of embodiment 1.
The preparation method of the semisolid lithium ion battery provided by the embodiment is the same as that of the embodiment 1, wherein the positive plate is the positive plate comprising the electronic insulating functional layer and the polymer electrolyte; the negative plate is a traditional negative electrode roll of a lithium ion battery in the industry, and the negative active material is a silicon-carbon negative electrode material.
Example 10
The battery pole piece of this example only includes the negative pole piece, and its preparation method is the same as that of example 1.
The preparation method of the semisolid lithium ion battery provided by the embodiment is the same as that of embodiment 1, wherein the positive plate is a conventional positive electrode roll of the lithium ion battery in industry, and the positive active material is ternary NCM811 (LiNi 0.83 Co 0.11 Mn 0.06 ) The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode sheet is a negative electrode sheet of this embodiment including an electronic insulating functional layer and a polymer electrolyte.
Comparative example 1
The comparative example provides a liquid lithium ion battery, the preparation method of which comprises the following steps:
(1) Respectively and uniformly mixing the positive and negative electrode active substances, the binder, the conductive agent and the solvent to prepare positive and negative electrode slurry, correspondingly and uniformly coating the positive and negative electrode slurry on the positive and negative electrode current collectors, drying, rolling and die cutting to obtain positive and negative electrode plates, wherein the specific preparation process is the same as that of the conventional common lithium ion battery electrode roll in the industry, and the positive electrode active material adopts ternary NCM811 (LiNi 0.83 Co 0.11 Mn 0.06 ) The negative electrode active material adopts a silicon-carbon negative electrode material.
(2) And preparing the prepared positive and negative electrode plates into a battery cell through a lamination process, wherein a diaphragm adopts a PP diaphragm, then placing the battery cell into a pit punching aluminum-plastic film, baking, injecting a silicon-carbon electrolyte, sealing, and standing to completely infiltrate the electrolyte. And after the infiltration is completed, performing chemical composition to obtain the liquid battery.
Comparative example 2
The preparation method of the battery pole piece provided in the comparative example is the same as that in example 1, except that: and (3) without the preparation process of the step (2), directly soaking the anode and cathode coils prepared in the step (1) in a polymer electrolyte precursor solution for in-situ solidification.
The preparation method of the semisolid lithium ion battery provided by the comparative example is the same as that of example 1.
Comparative example 3
The preparation method of the battery pole piece provided in the comparative example is the same as that in example 1, except that: and (3) and step (4) are omitted, and the positive and negative electrode sheets containing the active material layer and the electronic insulating functional layer are obtained.
The preparation method of the lithium ion battery provided in the comparative example is the same as the step (2) of the comparative example 1.
Comparative example 4
The battery pole piece provided in this comparative example is the same as comparative example 3.
The comparative example provides a solid-state lithium ion battery, the preparation method of which comprises:
the positive and negative electrode sheets prepared in comparative example 3 and containing the active material layer and the electronic insulating functional layer were fabricated into a battery cell by a lamination process, wherein the lamination process was the same as that of the conventional standard soft-pack battery, and the separator was a PP separator. And then placing the battery core in pit-punching aluminum plastic, baking, injecting the polymer electrolyte precursor solution prepared in the step (3) in the embodiment 1, keeping the injection process consistent with that of a standard soft-package battery, standing for 48 hours after the injection is finished, and curing in situ at 60 ℃ to obtain the solid-state lithium ion battery.
3 batteries of examples 1 to 10 and comparative examples 1 to 4 were prepared respectively, and were subjected to electrochemical performance and safety tests, wherein the design capacity of each battery cell was 2Ah, and the performance tests were as follows:
discharge capacity: the capacity expression rate is the ratio of the actual first-cycle discharge capacity to the theoretical capacity when tested at the room temperature of 25+/-2 ℃ and the 0.1C multiplying power.
Needling test: the battery is fully charged, a high temperature resistant steel needle with phi 3mm penetrates from the direction perpendicular to the battery polar plate at the speed of 20 mm/s, the penetrating position is preferably close to the geometric center of the penetrated surface, the steel needle stays in the battery, the battery is observed for one hour, the battery does not fire or explode to pass, and the surface temperature of the passing battery is recorded; each example and comparative cell protocol tested two cells.
Heating: putting the fully charged battery into a high-temperature test box, heating at a heating rate of 5 ℃/min, keeping constant temperature when the temperature in the box reaches (180+/-2) DEG C, and keeping for 30 minutes; in the test process, the battery does not fire or explode, and passes the test, otherwise, the battery passes the test.
Fig. 2 is a first-turn charge-discharge curve of the semi-solid battery of example 1, and it can be seen from the figure that the semi-solid lithium ion battery of this example is excellent in charge-discharge performance.
The results of the electrochemical performance tests (average test results of 3 cells) of the above-described batteries of examples 1 to 10 and comparative examples 1 to 4 are shown in table 1.
TABLE 1
From the test results in table 1, it is demonstrated that: the semi-solid lithium ion battery provided by the application shows excellent capacity performance, the discharge capacity of the semi-solid lithium ion battery is equivalent to that of the liquid battery in comparative example 1, meanwhile, the content of electrolyte is reduced, and the energy density of the battery is improved; the result of comparative example 1 shows that the liquid lithium ion battery has poor safety and cannot pass the needling and 180 ℃ hot box test; it can be seen from comparative example 2 that the needling safety and thermal stability of the battery can be improved to a certain extent by adopting the in-situ curing and solid electrolyte introduction strategy alone, and the needling passing rate and thermal safety of the battery can be greatly improved by combining the in-situ cured polymer solid electrolyte with the electronic insulating functional layer.
The test results of comparative example 4 show that the solid-state battery obtained by impregnating and solidifying the polymer electrolyte precursor solution after the positive and negative electrode sheet laminates are prepared into dry cells is poor in electrochemical performance because the electrolyte is difficult to form a continuous ion path inside the battery electrode sheet. In the application, the positive and negative electrode plates are soaked in the polymer electrolyte precursor solution, fully soaked and cured, and then the thickness of the electronic insulating functional layer, the particle size and the like are regulated and controlled, so that a uniform and rapid lithium ion passage is formed in the electrode plates, the problem that electrolyte is difficult to soak after the lamination of the battery electrode plates is avoided, and the performance of the multiplying power of the battery is ensured; meanwhile, the first liquid injection amount and the liquid retention amount can be reduced, and the energy density of the battery can be improved.
Fig. 3 shows a cycle stability graph of the semi-solid lithium ion battery prepared in example 1, showing excellent cycle stability. The values of the capacity retention after 100 cycles for comparative examples 1-10 and comparative examples 1-4 were found to be: the polymer electrolyte is introduced into the battery pole piece through in-situ solidification, so that the circulation stability of the battery can be improved, and the in-situ solidification can be used for adhering the polymer electrolyte into the pore canal of the pole piece, so that the battery pole piece has higher viscosity, and a good ion passage in the pole piece can be ensured even in the volume expansion process.
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, any of the above-described 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 (10)
1. The battery pole piece is characterized by comprising a current collector, an active material layer, an electronic insulating functional layer and a polymer electrolyte;
the active material layer is located between the current collector and the electronic insulating functional layer, and the polymer electrolyte is filled in pores of the active material layer and the electronic insulating functional layer.
2. The battery pole piece of claim 1, wherein at least one of the following conditions is satisfied:
a. the thickness of the electronic insulating functional layer is 1-20 mu m;
b. the electronic insulating functional layer comprises 70-95% of inorganic material and 5-30% of binder by mass percent;
c. the polymer electrolyte is obtained by in-situ polymerization of a polymer electrolyte precursor solution.
3. The battery pole piece of claim 2, wherein at least one of the following conditions is satisfied:
d. the inorganic material comprises a porous oxide material or an inorganic solid electrolyte material;
e. the binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber and cellulose;
f. the polymer electrolyte precursor solution includes: a polymerization monomer, lithium salt, an organic solvent and an initiator.
4. A battery pole piece as claimed in claim 3, wherein at least one of the following conditions is met:
g. the porous oxide material comprises at least one of magnesium oxide, zirconium dioxide, silicon dioxide, titanium dioxide and aluminum oxide;
h. the average particle diameter of the porous oxide material is 1-20 mu m;
i. the average pore diameter of the porous oxide material is 10nm-100nm;
j. the inorganic solid electrolyte material comprises at least one of a NASICON structure material, a garnet structure material and a perovskite structure material;
k. the NASICON structural material comprises Li 1+x Al x Ge 2-x (PO 4 ) 3 、Li 1+y Al y Ti 2-y (PO 4 ) 3 Based on Li 1+x Al x Ge 2-x (PO 4 ) 3 Is based on Li 1+y Al y Ti 2-y (PO 4 ) 3 Wherein 0.ltoreq.x.ltoreq. 0.75,0.ltoreq.y.ltoreq.0.5;
the garnet structure material comprises Li 7-a La 3 Zr 2-a O 12 And based on Li 7-a La 3 Zr 2-a O 12 Wherein 0.ltoreq.a.ltoreq.1;
m. the perovskite structure material comprises Li 3b La 2/3-b TiO 3 And based on Li 3b La 2/3-b TiO 3 Wherein b is 0.06.ltoreq.b.ltoreq.0.14;
the polymerization monomer comprises at least one of methyl methacrylate, ethylene carbonate, ethyl methacrylate, methoxy polyethylene glycol acrylate, glycidyl methacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylpropane triacrylate, polyethylene glycol diacrylate, ethylene carbonate, ethylene oxide and 1, 3-dioxolane;
the lithium salt comprises at least one of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonyl imide, lithium tetrafluoroborate and lithium hexafluoroarsenate;
the organic solvent comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, dimethoxymethane, gamma-butyrolactone and acetonitrile;
the initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl, dicumyl peroxide, dibenzoyl peroxide and ammonium persulfate.
5. The battery pole piece of any of claims 1-4, wherein when the battery pole piece is a positive pole piece, the active material layer comprises a positive active material comprising LiCoO 2 、LiNiO 2 、LiMnO 2 、LiNi p Co 1-p O 2 、LiNi p Co q Mn 1-p-q O 2 、LiNi p Co q Al 1-p-q O 2 Wherein 0.5.ltoreq.p < 1,0 < q < 0.5, and p+q=1;
when the battery pole piece is a negative pole piece, the raw material of the active material layer comprises a negative active material, and the negative active material comprises at least one of artificial graphite, natural graphite and silicon carbon negative electrode materials.
6. A method of making a battery pole piece according to any one of claims 1 to 5, comprising: coating slurry containing the active material layer raw material on at least one surface of the current collector to obtain a first pole piece;
coating the slurry containing the raw materials of the electronic insulating functional layer on the active material layer of the first pole piece to obtain a second pole piece;
and immersing the second electrode plate in the polymer electrolyte precursor solution, taking out, and then carrying out in-situ solidification to obtain the battery electrode plate.
7. The method of manufacturing according to claim 6, wherein at least one of the following conditions is satisfied:
the slurry containing the electronic insulating functional layer raw material comprises an inorganic material, a binder and a slurry solvent, wherein the slurry solvent comprises at least one of dimethylformamide, dimethylacetamide, diethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran;
s. before the in-situ curing, the method further comprises: removing excess polymer electrolyte precursor solution from the second electrode sheet surface;
and t, triggering the in-situ curing by adopting any one of heat, light and radiation.
8. The method according to claim 7, wherein the mass ratio of the inorganic material, the binder and the slurry solvent is (8-9.5): (0.5-3.5): (60-95).
9. The semi-solid lithium ion battery is characterized by comprising a positive plate and a negative plate; the positive electrode sheet and/or the negative electrode sheet adopts the battery electrode sheet of any one of claims 1-5.
10. The semi-solid state lithium ion battery of claim 9, further comprising a separator and an electrolyte, the separator and the electrolyte being located between the positive electrode sheet and the negative electrode sheet.
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