CN114883751A - Semi-solid battery and preparation method thereof - Google Patents

Semi-solid battery and preparation method thereof Download PDF

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Publication number
CN114883751A
CN114883751A CN202210607832.4A CN202210607832A CN114883751A CN 114883751 A CN114883751 A CN 114883751A CN 202210607832 A CN202210607832 A CN 202210607832A CN 114883751 A CN114883751 A CN 114883751A
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semi
safety
battery
coating
diaphragm
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李洋
曹子扬
朱冠楠
王义飞
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M10/058—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention provides a semi-solid battery, which comprises a high-safety ionic membrane, a negative plate, a positive plate and electrolyte; the high-safety ionic membrane is positioned between the negative plate and the positive plate; the electrolyte is positioned between the high-safety ionic membrane and the negative plate, and between the high-safety ionic membrane and the positive plate; the high-safety ionic membrane comprises a diaphragm, a first coating and a second coating, wherein the first coating is fixed on one side of the diaphragm, which is close to the negative plate, and the second coating is fixed on one side of the diaphragm, which is close to the positive plate; the first coating comprises a first functional material, and the first functional material is made of a material which can consume an electrolyte in situ to generate a stable layer; the second coating layer includes a second functional material made of a material capable of reacting with the active oxygen molecules. The invention has the beneficial effects that: the content of liquid electrolyte in the battery is reduced, and the electrolyte can react with active oxygen released by the anode material, so that the safety performance of the battery is greatly improved.

Description

Semi-solid battery and preparation method thereof
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a semi-solid battery comprising a high-safety ionic membrane and a preparation method thereof.
Background
With the occurrence of safety accidents of lithium ion batteries, the requirements of the industry on the safety performance of the lithium ion batteries are higher and higher; in the composition of lithium ion batteries, the diaphragm plays a very important role in the safety of lithium batteries; the conventional diaphragm is usually a high polymer porous membrane such as polyethylene, polypropylene and the like, but the high polymer porous membrane has poor heat resistance; therefore, ceramic (such as alumina, boehmite, etc.) is usually fixed on the surface of the separator to improve the heat resistance of the separator, but still higher safety requirements cannot be met.
A technology for improving the safety of a lithium ion battery by improving a separator has not been found at present; the prior art discloses improving the safety of lithium ion batteries by improving positive plates; for example, the publication No. CN 113540393A discloses a solid composite positive electrode, a preparation method thereof and a battery, which has a multilayer laminated structure including a first electrolyte layer, a first positive electrode active layer, a positive electrode current collector, a second positive electrode active layer and a second electrolyte layer, which are sequentially stacked; the first electrolyte layer, the first positive electrode active layer, the second positive electrode active layer and the second electrolyte layer all comprise inorganic solid electrolyte; on one hand, the process is to add a solid electrolyte into a positive electrode material and coat an electrolyte coating on the surface of the positive electrode material, and the addition of the solid electrolyte into the positive electrode can cause the content proportion of positive active substances to be reduced, the capacity of a battery to be reduced and the energy density to be reduced; on the other hand, because the surface of the positive electrode cannot reach the same flatness as the surface of the diaphragm, when micro gravure coating is adopted, the coating on the surface of the positive electrode can cause uneven local coating, pointed particles can appear, and the short circuit rate can be improved under a high-silicon system.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a semi-solid battery comprising a high-safety ionic membrane, which solves the problem that the safety of a lithium battery is improved by improving a positive plate in the prior art.
The invention solves the technical problems through the following technical means:
a semi-solid battery comprises a high-safety ionic membrane, a negative plate, a positive plate and electrolyte; the high-safety ionic membrane is positioned between the negative plate and the positive plate; the electrolyte is positioned between the high-safety ionic membrane and the negative plate, and between the high-safety ionic membrane and the positive plate; the high-safety ionic membrane comprises a diaphragm, a first coating and a second coating, wherein the first coating is fixed on one side, close to the negative plate, of the diaphragm, and the second coating is fixed on one side, close to the positive plate, of the diaphragm; the first coating comprises a first functional material made of a material capable of consuming an electrolyte in situ to generate a stable layer; the second coating layer includes a second functional material made of a material capable of reacting with active oxygen molecules.
Has the advantages that: the first functional material can generate a compact surface film layer through an oxidation-reduction reaction with the electrolyte in a lithium battery charging and discharging interval, so that the content of liquid electrolyte in the battery is reduced, and the heat resistance of the diaphragm can be improved through the generation of the surface film layer, thereby greatly improving the safety performance of the diaphragm and the battery; under the high temperature condition, when the positive electrode material takes place the phase transition and releases active oxygen, the second functional material can react with the active oxygen that releases, prevents the inside gaseous crosstalk of battery to avoid the emergence of thermal runaway, and then make the security of battery promote by a wide margin.
Preferably, the first functional material is one of a LLTO fast ion conductor and a LATP fast ion conductor.
Preferably, the second functional material is one of LLZO fast ion conductor and polydopamine.
Preferably, the first coating and the second coating each further comprise a dispersant, a thickener and a binder.
Preferably, the dispersant is an anionic dispersant.
Preferably, the thickener is sodium carboxymethyl cellulose or a mixed thickener taking sodium carboxymethyl cellulose as a main component.
Preferably, the binder is an acrylic binder.
Preferably, the separator is one or more of PE, PP, PI, cellulose, PET.
The invention also discloses a method for preparing the semi-solid battery in any technical scheme, which comprises the following steps:
s1, uniformly mixing and stirring the first functional material and the second functional material with a dispersant, a thickening agent and a binder, and respectively coating the mixture on two sides of a diaphragm to obtain a high-safety ionic membrane;
s2, stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate in sequence, and then injecting electrolyte to obtain a semi-finished product of the battery;
s3, the prepared semi-finished product of the battery is subjected to chemical composition and volume division under the conditions that the pressure is 600-1500kgf, the temperature is 25-45 ℃ and the multiplying power is 0.1-2C, so as to obtain the semi-solid battery.
Has the advantages that: the first functional material needs to be subjected to in-situ curing reaction at a low potential, the first functional material needs to be tightly attached to the negative electrode under the condition, and the low potential of the negative electrode is used for promoting the reaction, so that the contact between the first coating and the negative electrode is ensured by large pressure, and the first coating is in a low potential state.
Preferably, the method comprises the following steps:
s1 mixing and stirring the LATP fast ion conductor and the LLZO fast ion conductor with the sodium carboxymethyl cellulose, the acrylic acid and the anion dispersant uniformly, and respectively coating the mixture on two sides of the diaphragm to obtain a high-safety ion membrane;
s2 mixing SBR binder, SP conductive agent, and artificial graphite in a ratio of 2: 2: 96 is mixed fully in proportion to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
s3 mixing PVDF as binder, acetylene black as conductive agent and LiNi as ternary positive electrode material 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
s4, stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate in sequence, and injecting electrolyte with an injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
s5, the prepared semi-finished product of the battery is subjected to chemical composition and volume division under the conditions that the pressure is 1250kgf, the temperature is 35 ℃ and the multiplying power is 1C, and the semi-solid battery is obtained.
Has the advantages that: through the setting of the fast ionic conductor of LATP, the volume of consuming liquid electrolyte can reach 9g for the rete on diaphragm surface is thicker, thereby promotes the security performance of diaphragm and battery by a wide margin.
The invention has the advantages that:
according to the invention, through the arrangement of the first functional material and the second functional material, the first functional material can generate an oxidation-reduction reaction with the electrolyte in the charging and discharging interval of the lithium battery to generate a compact surface film layer, so that the content of the liquid electrolyte in the battery is reduced, and the heat resistance of the diaphragm can be improved through the generation of the surface film layer, thereby greatly improving the safety performance of the diaphragm and the battery; under the high temperature condition, when the positive electrode material takes place the phase transition and releases active oxygen, the second functional material can react with the active oxygen that releases, prevents the inside gaseous crosstalk of battery to avoid the emergence of thermal runaway, and then make the security of battery promote by a wide margin.
According to the invention, the component volume pressure is set to be 600-.
According to the invention, through the arrangement of the LATP fast ion conductor, the consumption of liquid electrolyte can reach 9g, so that the film layer on the surface of the diaphragm is thicker, and the safety performance of the diaphragm and the battery is greatly improved.
Drawings
FIG. 1 is a picture of a disassembled diaphragm in example 2;
FIG. 2 is a picture of a disassembled diaphragm in example 3;
FIG. 3 is a picture of a diaphragm disassembled in comparative example 1;
FIG. 4 is a photograph of a disassembled separator of comparative example 2;
FIG. 5 is a photograph of a disassembled separator of comparative example 3;
FIG. 6 is a graph showing the film formation effect on the negative electrode side of the separator in example 2;
fig. 7 is a graph showing the effect of film formation on the negative electrode side of the separator in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A semi-solid battery comprises a high-safety ionic membrane, a negative plate, a positive plate and electrolyte; the high-safety ionic membrane is positioned between the negative plate and the positive plate; the electrolyte is positioned between the high-safety ionic membrane and the negative plate, and between the high-safety ionic membrane and the positive plate; the high-safety ionic membrane comprises a diaphragm, a first coating and a second coating, wherein the first coating is fixed on one side of the diaphragm, which is close to the negative plate, and the second coating is fixed on one side of the diaphragm, which is close to the positive plate; the diaphragm is one or more of PE, PP, PI, cellulose and PET; the first coating comprises a first functional material, a dispersing agent, a thickening agent and a binder, wherein the first functional material is made of LLTO, LATP and other materials which can consume electrolyte in situ to generate a stable layer; the second coating comprises a second functional material, a dispersing agent, a thickening agent and a binder, wherein the second functional material is made of inorganic or organic materials such as LLZO, polydopamine and the like which can react with active oxygen molecules; the dispersant is an anionic dispersant, the thickener is sodium carboxymethyl cellulose or a mixed thickener taking the sodium carboxymethyl cellulose as a main component, and the binder is an acrylic acid binder.
The thickness of the diaphragm is 7-20 microns, the thickness of the coating is 1-4 microns, and the particle size of the functional material is 0.1-3 microns.
The first functional material can perform redox reaction with the electrolyte in the charging and discharging interval of the lithium battery to generate a compact surface film layer, so that the content of free liquid electrolyte in the full battery is reduced; under the high-temperature condition, when the anode material is subjected to phase change to release active oxygen, the second functional material can react with the released active oxygen to prevent gas crosstalk inside the battery, so that thermal runaway is avoided.
Example 2
A method of manufacturing a semi-solid battery, comprising the steps of:
(1) mixing and stirring the LATP fast ion conductor and the LLZO fast ion conductor with sodium carboxymethyl cellulose, acrylic acid and an anion dispersant uniformly, and respectively coating the mixture on two sides of a diaphragm to obtain a high-safety ion membrane;
(2) mixing a binder SBR, a conductive agent SP and artificial graphite in a ratio of 2: 2: 96 is mixed fully in proportion to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
(3) PVDF (polyvinylidene fluoride) binderElectrolyte acetylene black and ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
(4) sequentially stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate, and injecting electrolyte with an injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
(5) carrying out chemical composition and volume division on the prepared semi-finished product of the battery under 1250kgf pressurization, the ambient temperature of 35 ℃ and the multiplying power of 1C to obtain a semi-solid battery;
(6) and disassembling the semi-solid battery, weighing the diaphragm, performing surface analysis, observing the in-situ curing degree, and calculating to obtain the content of the residual liquid electrolyte.
Example 3
A method of manufacturing a semi-solid battery, comprising the steps of:
(1) mixing and stirring the LLTO fast ion conductor and the LLZO fast ion conductor with sodium carboxymethyl cellulose, acrylic acid and an anion dispersing agent uniformly, and respectively coating the mixture on two sides of a diaphragm to obtain a high-safety ionic membrane;
(2) mixing a binder SBR, a conductive agent SP and artificial graphite in a ratio of 2: 2: 96 is mixed fully in proportion to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
(3) PVDF as binder, acetylene black as conductive agent and LiNi as ternary positive electrode material 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
(4) sequentially stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate, and injecting electrolyte with an injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
(5) carrying out chemical composition and volume division on the prepared semi-finished product of the battery under 1250kgf pressurization, the ambient temperature of 35 ℃ and the multiplying power of 1C to obtain a semi-solid battery;
(6) and disassembling the semi-solid battery, weighing the diaphragm, performing surface analysis, observing the in-situ curing degree, and calculating to obtain the content of the residual liquid electrolyte.
Example 4
A method of manufacturing a semi-solid battery, comprising the steps of:
(1) mixing and stirring the LATP fast ion conductor and the LLZO fast ion conductor with sodium carboxymethyl cellulose, acrylic acid and an anion dispersant uniformly, and respectively coating the mixture on two sides of a diaphragm to obtain a high-safety ion membrane;
(2) mixing a binder SBR, a conductive agent SP and artificial graphite in a ratio of 2: 2: 96 is mixed fully to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
(3) PVDF as binder, acetylene black as conductive agent and LiNi as ternary positive electrode material 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
(4) sequentially stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate, and injecting electrolyte with an injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
(5) the prepared semi-finished product of the battery is subjected to chemical composition and volume division under 600kgf pressurization, 25 ℃ ambient temperature and 0.1C multiplying power to obtain a semi-solid battery;
(6) and disassembling the semi-solid battery, weighing the diaphragm, carrying out surface analysis, observing the in-situ curing degree, and calculating to obtain the content of the residual liquid electrolyte.
Example 5
A method of manufacturing a semi-solid battery, comprising the steps of:
(1) mixing and stirring the LATP fast ion conductor and the LLZO fast ion conductor with sodium carboxymethyl cellulose, acrylic acid and an anion dispersant uniformly, and respectively coating the mixture on two sides of a diaphragm to obtain a high-safety ion membrane;
(2) mixing a binder SBR, a conductive agent SP and artificial graphite in a ratio of 2: 2: 96 is mixed fully in proportion to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
(3) PVDF as binder, acetylene black as conductive agent and LiNi as ternary positive electrode material 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
(4) sequentially stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate, and injecting electrolyte with an injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
(5) carrying out formation and volume division on the prepared semi-finished product of the battery under 1500kgf pressurization, 45 ℃ ambient temperature and 2C multiplying power to obtain a semi-solid battery;
(6) and disassembling the semi-solid battery, weighing the diaphragm, performing surface analysis, observing the in-situ curing degree, and calculating to obtain the content of the residual liquid electrolyte.
Comparative example 1
A method of manufacturing a semi-solid battery, comprising the steps of:
(1) mixing and stirring the LATP fast ion conductor and the LLZO fast ion conductor with sodium carboxymethyl cellulose, acrylic acid and an anion dispersant uniformly, and respectively coating the mixture on two sides of a diaphragm to obtain a high-safety ion membrane;
(2) mixing a binder SBR, a conductive agent SP and artificial graphite in a ratio of 2: 2: 96 is mixed fully in proportion to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
(3) PVDF as binder, acetylene black as conductive agent and LiNi as ternary positive electrode material 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
(4) sequentially stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate, and injecting electrolyte with an injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
(5) carrying out chemical composition and volume division on the prepared semi-finished product of the battery under 500kgf pressurization, the environment temperature of 35 ℃ and the multiplying power of 1C to obtain a semi-solid battery;
(6) and disassembling the semi-solid battery, weighing the diaphragm, performing surface analysis, observing the in-situ curing degree, and calculating to obtain the content of the residual liquid electrolyte.
Comparative example 2
A method of making a battery comprising the steps of:
(1) mixing and stirring alumina ceramic, sodium carboxymethylcellulose, acrylic acid and an anionic dispersant uniformly, and respectively coating the mixture on two sides of a diaphragm to obtain a safety diaphragm;
(2) mixing a binder SBR, a conductive agent SP and artificial graphite in a ratio of 2: 2: 96 is mixed fully in proportion to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
(3) PVDF as binder, acetylene black as conductive agent and LiNi as ternary positive electrode material 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
(4) sequentially stacking and assembling the negative plate, the safety diaphragm and the positive plate, and injecting electrolyte with a liquid injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
(5) carrying out formation and partial capacity treatment on the prepared semi-finished product of the battery under 1250kgf pressurization, the environment temperature of 35 ℃ and the multiplying power of 1C to obtain the battery;
(6) and (3) disassembling the battery, weighing the diaphragm, carrying out surface analysis, observing the in-situ curing degree, and calculating to obtain the content of the residual liquid electrolyte.
Comparative example 3
A method of manufacturing a semi-solid battery, comprising the steps of:
(1) mixing and stirring boehmite, sodium carboxymethylcellulose, acrylic acid and an anionic dispersant uniformly, and respectively coating on two sides of a diaphragm to obtain a safety diaphragm;
(2) mixing a binder SBR, a conductive agent SP and artificial graphite in a ratio of 2: 2: 96 is mixed fully in proportion to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
(3) PVDF as binder, acetylene black as conductive agent and LiNi as ternary positive electrode material 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
(4) sequentially stacking and assembling the negative plate, the safety diaphragm and the positive plate, and injecting electrolyte with the injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
(5) carrying out formation and partial capacity treatment on the prepared semi-finished product of the battery under 1250kgf pressurization, the environment temperature of 35 ℃ and the multiplying power of 1C to obtain the battery;
(6) and (3) disassembling the battery, weighing the diaphragm, carrying out surface analysis, observing the in-situ curing degree, and calculating to obtain the content of the residual liquid electrolyte.
Table 1 shows the contents of the remaining liquid electrolytes after formation of the components in examples 2 to 5 and comparative examples 1 to 3.
Figure BDA0003672069230000101
Figure BDA0003672069230000111
Table 2 shows the safety tests of the batteries prepared in examples 2 to 5 and comparative examples 1 to 3, by keeping the temperature for more than 30 min.
Serial number Test standard (Battery hot box) Test results
Example 2 Heating to 150 deg.C at 5 deg.C/min, and maintaining for 30min By passing
Example 3 Heating to 150 deg.C at 5 deg.C/min, and maintaining for 30min By passing
Example 4 Heating to 150 deg.C at 5 deg.C/min, and maintaining for 30min By passing
Example 5 Heating to 150 deg.C at 5 deg.C/min, and maintaining for 30min By passing
Comparative example 1 Heating to 150 deg.C at 5 deg.C/min, and maintaining for 30min Keeping the temperature for 23min
Comparative example 2 Heating to 150 deg.C at 5 deg.C/min, and maintaining for 30min Keeping the temperature for 3min
Comparative example 3 Heating to 150 deg.C at 5 deg.C/min, and maintaining for 30min Keeping the temperature for 4min
As shown in table 1, the batteries prepared in examples 2 and 3 consumed liquid electrolyte in amounts of 9g and 7.6g, respectively, and as can be seen from fig. 1 and 2, the separators detached in examples 2 and 3 were black, and the liquid electrolyte generated a dense surface film layer (black) on the negative electrode side of the separator through the redox reaction with the first functional material, which not only reduced the content of the liquid electrolyte in the battery, but also improved the heat resistance of the separator through the generation of the surface film layer, thereby greatly improving the safety performance of the separator and the battery; as shown in table 1 and fig. 3, the battery prepared in comparative example 1 consumed 7g of liquid electrolyte, the removed separator was black and white, black was a surface film layer formed, and white was a separator, and the difference between comparative example 1 and example 2 was that the pressure applied during the formation of the separator was 500kgf, because the pressure was insufficient, the contact was not tight enough, and the curing reaction was not complete, resulting in black and white phases of the removed separator; as shown in fig. 4 and 5, the separators of comparative examples 2 and 3 were disassembled to be white, i.e., the batteries prepared in comparative examples 2 and 3 did not have a surface film layer formed on the separators thereof; as shown in FIG. 6, since the chemical composition volumetric pressure is in the range of 600-1500kgf, a dense surface film layer can be formed; as shown in FIG. 7, the formed surface film layer is not dense enough because the chemical component volumetric pressure is not in the range of 600-1500 kgf; the safety of the battery hot box is based on the retention time at high temperature, the longer the retention time is, the higher the safety of the battery is, the national standard test standard is 30min, as shown in table 2, examples 2 to 5 can pass the national standard test standard, comparative example 1 can keep the temperature for 23min because of insufficient pressure, and comparative examples 2 and 3 do not adopt high-safety ionic membranes, and the heat preservation can only reach 3min and 4 min.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A semi-solid battery is characterized by comprising a high-safety ionic membrane, a negative plate, a positive plate and electrolyte; the high-safety ionic membrane is positioned between the negative plate and the positive plate; the electrolyte is positioned between the high-safety ionic membrane and the negative plate, and between the high-safety ionic membrane and the positive plate;
the high-safety ionic membrane comprises a diaphragm, a first coating and a second coating, wherein the first coating is fixed on one side, close to the negative plate, of the diaphragm, and the second coating is fixed on one side, close to the positive plate, of the diaphragm;
the first coating comprises a first functional material made of a material capable of consuming an electrolyte in situ to generate a stable layer;
the second coating layer includes a second functional material made of a material capable of reacting with active oxygen molecules.
2. The semi-solid battery of claim 1, wherein the first functional material is one of a LLTO fast ion conductor, a LATP fast ion conductor.
3. The semi-solid battery according to claim 1, wherein the second functional material is one of a LLZO fast ion conductor, polydopamine.
4. The semi-solid state battery of claim 1, wherein the first coating layer and the second coating layer each further comprise a dispersant, a thickener, and a binder.
5. The semi-solid battery of claim 4, wherein the dispersant is an anionic dispersant.
6. The semi-solid battery according to claim 4, wherein the thickener is sodium carboxymethyl cellulose or a mixed thickener having sodium carboxymethyl cellulose as a main component.
7. The semi-solid battery of claim 4, wherein the binder is an acrylic binder.
8. The semi-solid state battery of claim 1, wherein the separator is one or more of PE, PP, PI, cellulose, PET.
9. A method of manufacturing the semi-solid battery of any one of claims 1-8, comprising the steps of:
s1, uniformly mixing and stirring the first functional material and the second functional material with a dispersant, a thickening agent and a binder, and respectively coating the mixture on two sides of a diaphragm to obtain a high-safety ionic membrane;
s2, stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate in sequence, and then injecting electrolyte to obtain a semi-finished product of the battery;
s3, the prepared semi-finished product of the battery is subjected to chemical composition and volume division under the conditions that the pressure is 600-1500kgf, the temperature is 25-45 ℃ and the multiplying power is 0.1-2C, so as to obtain the semi-solid battery.
10. The method for preparing the semi-solid battery according to claim 9, comprising the steps of:
s1 mixing and stirring the LATP fast ion conductor and the LLZO fast ion conductor with the sodium carboxymethyl cellulose, the acrylic acid and the anion dispersant uniformly, and respectively coating the mixture on two sides of the diaphragm to obtain a high-safety ion membrane;
s2 mixing SBR binder, SP conductive agent, and artificial graphite in a ratio of 2: 2: 96 is mixed fully in proportion to prepare slurry, the slurry is coated on a copper foil with the thickness of 6 mu m, the copper foil is baked and dried at the temperature of 120 ℃, and the negative plate is obtained by rolling;
s3 mixing PVDF as binder, acetylene black as conductive agent and LiNi as ternary positive electrode material 0.8 Co 0.1 Mn 0.1 O 2 And (3) adding the following components in percentage by weight of 2: 3: 95, uniformly coating the obtained slurry on an aluminum foil with the thickness of 12 mu m, baking at the temperature of 120 ℃, and rolling to obtain a positive plate;
s4, stacking and assembling the negative plate, the high-safety ionic membrane and the positive plate in sequence, and injecting electrolyte with an injection coefficient of 2.0g/Ah to obtain a semi-finished product of the battery;
s5, the prepared semi-finished product of the battery is subjected to chemical composition and volume division under the conditions that the pressure is 1250kgf, the temperature is 35 ℃ and the multiplying power is 1C, and the semi-solid battery is obtained.
CN202210607832.4A 2022-05-31 2022-05-31 Semi-solid battery and preparation method thereof Pending CN114883751A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110495037A (en) * 2017-03-28 2019-11-22 （株）七王能源 The composite electrolyte of multilayered structure and the secondary cell for using it
CN110600664A (en) * 2019-10-25 2019-12-20 苏州清陶新能源科技有限公司 Battery diaphragm, preparation method thereof and battery comprising battery diaphragm
CN112688022A (en) * 2020-12-28 2021-04-20 安普瑞斯（无锡）有限公司 Quick charge-discharge lithium ion battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110495037A (en) * 2017-03-28 2019-11-22 （株）七王能源 The composite electrolyte of multilayered structure and the secondary cell for using it
CN110600664A (en) * 2019-10-25 2019-12-20 苏州清陶新能源科技有限公司 Battery diaphragm, preparation method thereof and battery comprising battery diaphragm
CN112688022A (en) * 2020-12-28 2021-04-20 安普瑞斯（无锡）有限公司 Quick charge-discharge lithium ion battery and preparation method thereof

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Application publication date: 20220809