CN111799513A - Diaphragm-free quasi-solid battery and preparation method of composite pole piece thereof - Google Patents
Diaphragm-free quasi-solid battery and preparation method of composite pole piece thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
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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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a diaphragm-free quasi-solid battery and a preparation method of a composite pole piece of the diaphragm-free quasi-solid battery. The invention has the following advantages and effects: the surface of the negative plate is coated with the inorganic solid electrolyte layer and then coated with the organic polymer layer to replace a diaphragm, so that on one hand, the inorganic solid electrolyte layer has the lithium ion conduction function and high strength, and the conductivity and mechanical strength of the lithium ion battery are improved; on the other hand, the organic polymer layer has the function of thermal shutdown coating, pores among particles at normal temperature can ensure smooth reciprocating interpenetration of lithium ions, melting collapse of coating particles is realized at higher temperature, lithium ions are isolated from passing through, and the safety performance of the lithium ion battery is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a diaphragm-free quasi-solid battery and a preparation method of a composite pole piece of the diaphragm-free quasi-solid battery.
Background
As a new generation of chemical power source, lithium ion batteries are widely used in mobile phones, notebook computers and other digital electronic products, have been expanded to the fields of electric bicycles/motorcycles, electric vehicles and the like, are also used in the fields of aerospace, navigation, artificial satellites, medical treatment, military communication equipment and the like, and gradually replace traditional batteries.
The structure of the lithium ion battery commercially used at present mainly comprises a positive electrode, a negative electrode and a diaphragm, wherein the diaphragm is a specially formed polymer film with a microporous structure, and the diaphragm is mainly used for separating the positive electrode and the negative electrode of the battery and allowing lithium ions to freely pass through but not allowing electrons to pass through. The battery diaphragm has the function of isolating the positive electrode and the negative electrode, prevents the explosion caused by the short circuit of the battery, plays an important role in the safety performance of the lithium ion battery, is made of organic polymer materials at present, and has some problems, on one hand, when the battery or a battery system is abnormally heated, the materials can shrink, melt or even carbonize, and the large-area contact of the positive electrode and the negative electrode can be caused to cause the short circuit or even the explosion; on the other hand, impurities and burrs in the battery can pierce through the diaphragm to cause direct contact of the positive and negative electrode plates to cause short circuit.
At present, a patent with publication number CN105958112A discloses a lithium ion battery roll core without a diaphragm and a preparation method thereof, which comprises a positive plate and a negative plate, wherein a functional coating is coated on both surfaces of at least one of the positive plate and the negative plate; the functional coating is formed by mixing polyvinylidene fluoride, polymethyl methacrylate and polyacrylonitrile.
The above prior art solutions have the following drawbacks: although the above patent covers the functional coating formed by mixing polyvinylidene fluoride, polymethyl methacrylate and polyacrylonitrile on the two sides of at least one of the positive plate and the negative plate, and uses the functional coating to replace a diaphragm to realize no diaphragm, polyvinylidene fluoride is not stable enough for the negative electrode, and polymethyl methacrylate is dissolved in electrolyte, so that the problems still exist in the practical application of the battery, and therefore, the improvement still remains.
Disclosure of Invention
In view of the defects of the prior art, a first object of the present invention is to provide a quasi-solid battery without a separator, which can avoid the problems that polyvinylidene fluoride is not stable enough to a negative electrode and polymethyl methacrylate is dissolved in an electrolyte.
In order to achieve the purpose, the invention provides the following technical scheme:
the utility model provides a no diaphragm's accurate solid-state battery, includes positive plate, compound pole piece and the wetting additive in interface, compound pole piece includes negative plate, inorganic solid state electrolyte layer and organic polymer layer, inorganic solid state electrolyte layer coats in the two-sided of negative plate, just organic polymer layer coats in the surface on inorganic solid state electrolyte layer.
By adopting the technical scheme, the surface of the negative plate is coated with the inorganic solid electrolyte layer and then coated with the organic polymer layer to replace a diaphragm, so that on one hand, the inorganic solid electrolyte layer has the lithium ion conduction function and high strength, and the conductivity and mechanical strength of the lithium ion battery are improved; on the other hand, the organic polymer layer has the function of thermal shutdown coating, pores among particles at normal temperature can ensure smooth reciprocating interpenetration of lithium ions, melting collapse of coating particles is realized at a higher temperature (80-150 ℃) to isolate the lithium ions from passing through, further occurrence of chemical reaction is blocked, safety performance of the lithium ion battery is improved, meanwhile, the organic polymer coating can increase bonding with a positive plate, and the problems that polyvinylidene fluoride is not stable enough to a negative electrode, polymethyl methacrylate is dissolved in electrolyte and the like are avoided.
The present invention in a preferred example may be further configured to: the inorganic solid electrolyte layer comprises the following components in parts by weight:
30-43 parts of inorganic solid electrolyte powder;
0.2-0.7 part of dispersant;
1-5 parts of a binder;
50-70 parts of an organic solvent;
the inorganic solid electrolyte powder is NASICON type solid electrolyte Li1+xTi2-xMx(PO4)3、Li1+xGe2-xMx(PO4)3(0.1<x<0.7, M = Al, Ga, In, Sc); perovskite solid electrolyte Li3xLa(2/3)-xTiO3(0<x<0.16); LISICON type solid electrolyte Li14ZnGe4O16(ii) a Garnet-type solid electrolyte Li5La3M2O12,(M=Ta，Nb)、Li7La3Zr2O12At least one of (1).
By adopting the technical scheme, the inorganic solid electrolyte layer with lithium ion conduction function and high strength is prepared, and the conductivity and mechanical strength of the lithium ion battery are improved.
The present invention in a preferred example may be further configured to: the thickness of the inorganic solid electrolyte layer is 5-10 μm.
By adopting the technical scheme, the thickness of the inorganic solid electrolyte layer mainly depends on the coating effect of the coating, the smaller the thickness of the inorganic electrolyte layer is, the greater the probability of coating missing is, but the thinner the coating is, the battery quality can be reduced, which is equivalent to improving the energy density. Therefore, the requirement on the thickness of the coating is to reduce the thickness of the coating as much as possible on the premise of ensuring that the coating does not leak; experiments prove that when the thickness of the inorganic solid electrolyte layer is 5-10 mu m, the coating can be ensured to be free from missing coating, the quality of the battery can be reduced, and the energy density can be improved.
The present invention in a preferred example may be further configured to: the thickness of the organic polymer layer is 1-3 μm; and the organic polymer layer comprises the following components in parts by weight:
25-40 parts of an organic polymer;
3-7 parts of acrylic resin binder;
53-72 parts of deionized water;
the organic polymer is at least one of EVA, PVDF and PS.
By adopting the technical scheme, the thickness of the organic polymer layer is related to the surface appearance of the coating and the internal resistance value of the battery: the thickness is too low, the inorganic solid electrolyte coating can be exposed on the surface of the coating, and the effects of melting collapse and blocking the conduction of the battery at high temperature cannot be achieved; the thickness is too large, the internal resistance is increased, the self heat loss is increased, the performance of the battery is deteriorated, and the problem of mismatching after the battery is connected with other batteries in series is caused, so that the capacity and the performance of the whole battery pack are reduced.
The present invention in a preferred example may be further configured to: the organic polymer layer is a spherical granular organic polymer layer.
By adopting the technical scheme, the spherical polymer layer can form pores among the particles, can ensure smooth reciprocating interpenetration of lithium ions, and is mainly a structure which can be fused and collapsed to play a role in blocking.
The present invention in a preferred example may be further configured to: the negative plate is a graphite layer or a silicon-carbon layer or a lithium titanate layer coated on two sides of a copper foil and a lithium foil or lithium alloy negative electrode; the positive plate is an aluminum foil coated with a lithium-rich material on two sides, and the lithium-rich material is one of lithium iron phosphate, an NCM ternary material, an NCA ternary material, lithium manganate or lithium cobaltate.
By adopting the technical scheme, the battery is prepared by adopting the positive plate and the negative plate.
The present invention in a preferred example may be further configured to: the interface wetting additive comprises one or more of electrolyte formed by dissolving lithium metal salt in a solvent, molten salt electrolyte formed by compounding the lithium metal salt with other compounds or lithium metal salt alone, and ionic liquid electrolyte.
By adopting the technical scheme, the interface wetting additive is adopted to assist in the smooth preparation of the battery.
The second purpose of the invention is to provide a preparation method of the composite pole piece of the diaphragm-free quasi-solid battery.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation method of a composite pole piece of a diaphragm-free quasi-solid battery comprises the following steps:
(1) mixing inorganic solid electrolyte powder, a dispersing agent, a binder and an organic solvent, and preparing inorganic solid electrolyte slurry through high-speed shearing dispersion or ball milling or sanding dispersion, wherein the stirring speed of the high-speed shearing dispersion is 800-1200 rpm; the rotating speed of the double planetary ball milling is 250-350 rpm; the sanding rotating speed is 1400-1800 rpm;
(2) compounding the inorganic solid electrolyte slurry on the surface of the negative plate by a coating method to form a coating layer, and drying the coating layer to obtain an inorganic coating;
(3) preparing organic polymer slurry by high-speed shearing dispersion or ball milling or sanding dispersion of an organic polymer, an acrylic resin binder and deionized water, wherein the stirring speed of the high-speed shearing dispersion is 800-1200 rpm; the rotating speed of the double planetary ball milling is 250-350 rpm; the sanding rotating speed is 1400-1800 rpm;
(4) and compounding the organic polymer slurry on the surface of the inorganic solid electrolyte layer by a coating method to form a coating layer, and drying the coating layer to obtain the coating.
The present invention in a preferred example may be further configured to: the coating method comprises at least one of micro-concave coating, extrusion coating, transfer coating, screen printing, electrostatic spraying, atomized spraying, casting and 3D printing; when the organic polymer is oily slurry, spraying by at least one of electrostatic spraying and atomized spraying to obtain a spherical granular organic polymer layer; when the organic polymer is an aqueous slurry, coating by at least one of the coating methods described results in a spherical particulate organic polymer layer.
By adopting the technical scheme, at least one method of micro-concave coating, extrusion coating, transfer coating, screen printing, spraying, tape casting and 3D printing is adopted, so that convenient coating operation is realized; and the spherical granular organic polymer layer is obtained by adopting a corresponding mode aiming at the water-based or oil-based organic polymer.
The present invention in a preferred example may be further configured to: in the step (3), the organic polymer slurry may be prepared by dissolving 10 to 30 parts of the organic polymer in 70 to 90 parts of NMP solvent with stirring.
By adopting the technical scheme, the organic polymer slurry can also be prepared by mixing the organic polymer and the NMP solvent.
In summary, the invention includes at least one of the following beneficial technical effects:
1. the surface of the negative plate is coated with the inorganic solid electrolyte layer and then coated with the organic polymer layer to replace a diaphragm, so that on one hand, the inorganic solid electrolyte layer has the lithium ion conduction function and high strength, and the conductivity and mechanical strength of the lithium ion battery are improved; on the other hand, the organic polymer layer has the function of thermal shutdown coating, pores among particles can ensure smooth reciprocating penetration of lithium ions at normal temperature, melting collapse of coating particles is realized at higher temperature to isolate the lithium ions from passing through, the safety performance of the lithium ion battery is improved, and the problems that polyvinylidene fluoride is not stable enough to a negative electrode, polymethyl methacrylate is dissolved in electrolyte and the like are avoided;
2. the inorganic solid electrolyte layer has the lithium ion conduction function and high strength, and the conductivity and the mechanical strength of the lithium ion battery are improved;
3. the spherical granular organic polymer layer has the function of thermal shutdown coating, pores among granules can ensure smooth reciprocating penetration of lithium ions at normal temperature, melting collapse of coating granules is realized at higher temperature (80-150 ℃) to isolate the lithium ions from passing through, further generation of chemical reaction is blocked, and the safety performance of the lithium ion battery is improved; aiming at the water-based or oil-based organic polymer, obtaining a spherical granular organic polymer layer in a corresponding mode;
4. the organic polymer coating can increase the adhesion with the positive plate.
Drawings
FIG. 1 is a schematic structural diagram of a composite pole piece provided by the present invention;
FIG. 2 is a LLZO layer in example 1 of the present invention;
FIG. 3 is a PVDF layer in example 1 of the present invention;
FIG. 4 is a graph of a normal charge and discharge curve of a battery according to example 1 of the present invention;
fig. 5 is a short circuit diagram of the battery of comparative example 2 of the present invention.
The reference signs are: 1. a negative current collector; 2. a negative plate; 3. an inorganic solid electrolyte layer; 4. an organic polymer layer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Examples
Example 1
As shown in fig. 1, the preparation method of the quasi-solid state battery includes the following steps:
1) preparing a positive plate and a negative plate:
preparing a positive plate: (A) mixing a positive electrode active material, a conductive agent and a binder in a NMP solvent according to a mass ratio m (NCM523): m (SP): m (PVDF) =92.5:4:3.5 to prepare positive electrode slurry; (B) coating the positive electrode slurry on the two sides of the aluminum foil current collector on a slit extrusion coating machine, and drying to obtain a positive electrode plate;
preparing a negative plate: (A) mixing a negative electrode active material, a conductive agent, a dispersing agent and a binder in a mass ratio of m (graphite), m (SP), m (CMC), m (SBR), 96.4:0.8:1:1.8 in deionized water to prepare negative electrode slurry; (B) coating the negative slurry on the two sides of a copper foil current collector, namely a negative current collector 1, on a slit extrusion coating machine, and drying to obtain a negative plate 2;
2) preparing inorganic solid electrolyte slurry for coating: mixing 35 parts of inorganic solid electrolyte powder LLZO, 0.35 part of castor oil, 3 parts of binder EVA and 61.65 parts of xylene, and preparing inorganic solid electrolyte slurry by sanding and dispersing at the rotating speed of 1400 rpm;
3) the first surface of the negative plate 2 is chemically coated: coating the LLZO slurry prepared in the step 2) on the finished negative plate 2 prepared in the step 1) on a micro-gravure coating machine in a double-sided manner, and drying to obtain an LLZO layer, namely an inorganic solid electrolyte layer 3, wherein the SEM of the LLZO layer is shown in figure 2; and the thickness of the inorganic solid dielectric layer is 5 μm;
4) preparing organic polymer slurry for coating: dispersing 30 parts of PVDF, 3 parts of dispersant BYK-LPC 22136, 6 parts of ethyl acrylate and 61 parts of deionized water by sanding at the rotating speed of 1800rpm to prepare organic polymer slurry;
5) and (3) chemically coating the surface of the negative plate 2 for the second time: coating the PVDF aqueous slurry prepared in the step 4) on the negative plate 2 prepared in the step 3) on the two sides of a concave coating machine, drying to obtain a spherical granular PVDF layer, namely an organic polymer layer 4, wherein the thickness of the organic polymer layer 4 is 1 mu m, and the SEM of the organic polymer layer is shown in figure 3 to obtain a composite plate;
6) cutting the positive plate in the step 1) and the composite plate in the step 5) to the size required by the design battery;
7) wetting the interface with an additive LiPF6dripping-PC-EC-TTFP solution on the positive plate and the composite plate in the step 6), and standing for 10 minutes to ensure that LiPF is added6the-PC-EC-TTFP solution enters the pores of the pole piece and infiltrates active material particles; interfacial wetting additive LiPF6LiPF in-PC-EC-TTFP solution6Concentration of 1mol/L, TTFP content of 5wt%, PC: EC volume ratio =1:1, liquid at room temperature;
8) and (3) manufacturing the pole pieces in the step 7) into a battery cell in a lamination mode, and then performing tab welding, packaging and pre-charging to obtain the quasi-solid battery.
When the inorganic solid electrolyte layer is 5 μm and the organic polymer layer is 1 μm thick, the battery is normally charged and discharged as shown in fig. 4.
Example 2
As shown in fig. 1, the preparation method of the quasi-solid state battery includes the following steps:
1) preparing a positive plate and a negative plate:
preparing a positive plate: (A) mixing a positive electrode active material, a conductive agent and a binder in a NMP solvent according to a mass ratio m (NCM811) m (SP) m (PVDF) =92.5:4:3.5 to prepare positive electrode slurry; (B) coating the positive electrode slurry on the two sides of the aluminum foil current collector on a slit extrusion coating machine, and drying to obtain a positive electrode plate;
preparing a negative plate: (A) mixing a negative electrode active material, a conductive agent, a dispersing agent and a binder in a mass ratio of m (silicon carbon), m (SP), m (CMC), m (SBR), 95.7:1:1.3:2 in deionized water to prepare negative electrode slurry; (B) coating the negative electrode current collector 1 on the double surfaces of a transfer coating machine with negative electrode slurry, and drying to obtain a negative electrode piece 2;
2) preparing inorganic solid electrolyte slurry for coating: mixing 30 parts of inorganic solid electrolyte powder LATP, 3 parts of binder PVDF and 67 parts of NMP, and preparing inorganic solid electrolyte slurry by ball milling dispersion at the rotating speed of 250 rpm;
3) the first surface of the negative plate 2 is chemically coated: coating the prepared LATP slurry in the step 2) on the finished negative plate 2 prepared in the step 1) on a micro-concave coating machine on two sides, and drying to obtain an LATP layer, namely an inorganic solid electrolyte layer 3; and the thickness of the inorganic solid dielectric layer is 10 μm;
4) preparing organic polymer slurry for coating: mixing 15 parts of EVA and 85 parts of dimethylbenzene, and stirring to prepare organic polymer slurry;
5) and (3) chemically coating the surface of the negative plate 2 for the second time: spraying the EVA slurry prepared in the step 4) on the negative pole piece 2 prepared in the step 3) in a double-sided manner by adopting an electrostatic spraying manner, and drying to obtain an EVA layer, namely an organic polymer layer 4, wherein the thickness of the organic polymer layer 4 is 3 microns, so as to obtain a composite pole piece;
6) cutting the positive plate in the step 1) and the composite plate in the step 5) to the size required by the design battery;
7) wetting the interface with an additive LiPF6Dripping a PC-EC-TTFP solution on the positive plate and the composite plate in the step 6), standing for 2 minutes to enable the interface wetting additive to enter pores of the plate, and infiltrating active material particles; interfacial wetting additive LiPF6LiPF in-PC-EC-TTFP solution6Concentration of 1mol/L, TTFP content of 5wt%, PC: EC volume ratio =1:1, liquid at room temperature;
8) and (3) manufacturing the pole piece in the step 7) into a battery cell in a winding mode, and then performing tab welding, packaging and pre-charging to obtain the quasi-solid battery.
Example 3
As shown in fig. 1, the preparation method of the quasi-solid state battery includes the following steps:
1) preparing a positive plate and a negative plate:
preparing a positive plate: (A) mixing a positive electrode active material, a conductive agent and a binder in a NMP solvent according to a mass ratio m (NCM523): m (SP): m (PVDF) =92.5:4:3.5 to prepare positive electrode slurry; (B) coating the positive electrode slurry on the two sides of the aluminum foil current collector on a slit extrusion coating machine, and drying to obtain a positive electrode plate;
preparing a negative plate: (A) mixing a negative electrode active material, a conductive agent, a dispersing agent and a binder in a mass ratio of m (graphite), m (SP), m (CMC), m (SBR), 96.4:0.8:1:1.8 in deionized water to prepare negative electrode slurry; (B) coating the negative electrode current collector 1 on the double surfaces of a slit extrusion coating machine with negative electrode slurry, and drying to obtain a negative electrode piece 2;
2) preparing inorganic solid electrolyte slurry for coating: mixing 40 parts of inorganic solid electrolyte powder LAGP, 0.3 part of castor oil, 5 parts of binder PVDF and 54.7 parts of DMF, and preparing inorganic solid electrolyte slurry by sanding and dispersing at the rotating speed of 1600 rpm;
3) the first surface of the negative plate 2 is chemically coated: coating the prepared LAGP slurry in the step 2) on the finished negative plate 2 prepared in the step 1) on two sides of a micro-gravure coating machine, and drying to obtain an LAGP layer, namely an inorganic solid electrolyte layer 3; and the thickness of the inorganic solid dielectric layer is 7 μm;
4) preparing organic polymer slurry for coating: dispersing 10 parts of PS and 90 parts of NMP by high-speed shearing at the stirring speed of 800rpm to prepare organic polymer slurry;
5) and (3) chemically coating the surface of the negative plate 2 for the second time: coating the PS slurry prepared in the step 4) on the negative plate 2 prepared in the step 3) on a casting machine at two sides, and drying to obtain a PS layer, namely an organic polymer layer 4, wherein the thickness of the organic polymer layer 4 is 2 microns, so as to obtain a composite plate;
6) cutting the positive plate in the step 1) and the composite plate in the step 5) to the size required by the design battery;
7) wetting the interface with an additive LiPF6Dripping a PC-EC-TTFP solution on the positive plate and the composite plate in the step 6), standing for 8 minutes to enable the interface wetting additive to enter pores of the plate, and infiltrating active material particles; interfacial wetting additive LiPF6LiPF in-PC-EC-TTFP solution6Concentration of 1mol/L, TTFP content of 5wt%, PC: EC volume ratio =1:1, room temperatureIs in liquid state;
8) and (3) manufacturing the pole pieces in the step 7) into a battery cell in a lamination mode, and then performing tab welding, packaging and pre-charging to obtain the quasi-solid battery.
Comparative example
Comparative example 1
1) Preparing a positive plate and a negative plate:
preparing a positive plate: (A) mixing a positive electrode active material, a conductive agent and a binder in a NMP solvent according to a mass ratio m (NCM523): m (SP): m (PVDF) =92.5:4:3.5 to prepare positive electrode slurry; (B) coating the positive electrode slurry on the two sides of the aluminum foil current collector on a slit extrusion coating machine, and drying to obtain a positive electrode plate;
preparing a negative plate: (A) mixing a negative electrode active material, a conductive agent, a dispersing agent and a binder in a mass ratio of m (graphite), m (SP), m (CMC), m (SBR), 96.4:0.8:1:1.8 in deionized water to prepare negative electrode slurry; (B) coating the negative electrode current collector 1 on the double surfaces of a slit extrusion coating machine with negative electrode slurry, and drying to obtain a negative electrode piece 2;
2) cutting the positive plate in the step 1) and the negative plate in the step 2) to the size required by the design battery;
3) cutting the PE diaphragm to a size required by design;
4) wetting the interface with an additive LiPF6Dripping a PC-EC-TTFP solution on the positive plate and the negative plate in the step 2), standing for 10 minutes to enable an interface wetting additive to enter pores of the plates, and infiltrating active material particles; interfacial wetting additive LiPF6LiPF in-PC-EC-TTFP solution6Concentration of 1mol/L, TTFP content of 5wt%, PC: EC volume ratio =1:1, liquid at room temperature;
5) and (3) preparing the pole piece in the step 4) and the diaphragm in the step 3) into a battery cell in a lamination mode, and then carrying out tab welding, packaging and pre-charging to obtain the quasi-solid battery.
Comparative example 2
As shown in fig. 5, the difference from example 1 is that the inorganic solid electrolyte layer has a thickness of 4 μm, and the test shows a short-circuit condition, and the battery cannot be charged.
Comparative example 3
The difference from example 1 is that the inorganic solid electrolyte layer has a thickness of 11 μm, and the coating layer is heavy at this time, resulting in a decrease in the energy density of the battery.
Comparative example 4
The difference from example 1 is that the organic polymer layer has a thickness of 4 μm, and the coating layer is heavy at this time, resulting in a decrease in the energy density of the battery.
Performance test
The test method comprises the following steps:
(1) and (3) testing the adhesive force: the 3M adhesive tape was attached to the surface of the negative electrode sheet, a sample having a width of 10mm was cut, the adhesive tape was peeled off at an angle of 180 ° and at a speed of 50mm/min on a tensile testing machine, and the peel strength was measured as the peel strength obtained by dividing the peel force by the sample width, and the results are shown in attached table 1.
(2) Interface impedance: the button cell is composed of the positive and negative electrode sheets prepared according to the procedures described in the examples and comparative examples, and the interface wetting additive is added to carry out the AC impedance test with the test frequency of 0.01-106Hz, and the results are shown in the attached Table 1.
(3) Heat shutdown temperature: and manufacturing a test battery, and connecting a lead at the position of the lug to test the resistance of the battery. And then the battery is put into an environment with the temperature rising from 30 ℃ to 200 ℃ and the temperature rising rate of 5 ℃/min for heating and temperature rising, and the temperature value of the test battery and the resistance value corresponding to the temperature value are recorded every 5 s. In the process, the resistance value is increased and then decreased until the decrease of the resistance value is less than 1 omega every 5s, and the test is terminated. And drawing a temperature-resistance curve according to the obtained data, and calculating a resistance difference value every 5s, wherein the temperature corresponding to the first time when the resistance value rises to exceed 50 omega is the thermal shutdown temperature of the test diaphragm of the test battery, and the result is shown in the attached table 1.
TABLE 1 measurement results of electrode sheet with electrolyte layer for each example and comparative example
| Test items | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Adhesion test/N/m | 68 | 67 | 64 | 48 |
| Interface impedance/omega | 65 | 66 | 64 | 93 |
| Heat shut-off temperature/. degree.C | 160 | 70 | 145 | 135 |
In conclusion, as can be seen from the comparison of the data of the examples and comparative example 1, the batteries having different thermal shutdown temperatures can be obtained by coating the inorganic solid electrolyte layer on the surface of the negative electrode sheet and then coating the organic polymer layer thereon. Meanwhile, example 1 also showed stronger peel strength compared to comparative example 1, thereby also demonstrating better performance by recoating an organic polymer layer on the inorganic solid electrolyte layer. In addition, it is seen from the measurement results that the interface resistance of the composite electrolyte layer of example 1 is also small.
It can be seen from the comparison of example 1 and comparative examples 2 to 4 that the battery has better performance when the thickness of the inorganic solid electrolyte layer is between 5 and 10 μm and the thickness of the organic polymer layer is between 1 and 3 μm.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (10)
1. A diaphragm-free quasi-solid state battery, characterized by: the composite electrode plate comprises a negative electrode plate, a composite electrode plate and an interface wetting additive, wherein the composite electrode plate comprises a negative electrode plate, an inorganic solid electrolyte layer and an organic polymer layer, the inorganic solid electrolyte layer is coated on the two sides of the negative electrode plate, and the organic polymer layer is coated on the surface of the inorganic solid electrolyte layer.
2. The quasi-solid battery of claim 1, wherein: the inorganic solid electrolyte layer comprises the following components in parts by weight:
30-43 parts of inorganic solid electrolyte powder;
0.2-0.7 part of dispersant;
1-5 parts of a binder;
50-70 parts of an organic solvent;
the inorganic solid electrolyte powder is NASICON type solid electrolyte Li1+xTi2-xMx(PO4)3、Li1+xGe2-xMx(PO4)3（0.1<x<0.7, M = Al, Ga, In, Sc); perovskite solid electrolyte Li3xLa(2/3)-xTiO3(0<x<0.16); LISICON type solid electrolyte Li14ZnGe4O16(ii) a Garnet-type solid electrolyte Li5La3M2O12,(M=Ta，Nb)、Li7La3Zr2O12At least one of (1).
3. The quasi-solid battery of claim 2, wherein: the thickness of the inorganic solid electrolyte layer is 5-10 μm.
4. The quasi-solid battery of claim 1, wherein: the thickness of the organic polymer layer is 1-3 μm; and the organic polymer layer comprises the following components in parts by weight:
25-40 parts of an organic polymer;
3-7 parts of acrylic resin binder;
53-72 parts of deionized water;
the organic polymer is at least one of EVA, PVDF and PS.
5. The quasi-solid battery of claim 4, wherein: the organic polymer layer is spherical particles.
6. The quasi-solid battery of claim 1, wherein: the negative plate is a graphite layer or a silicon-carbon layer or a lithium titanate layer coated on two sides of a copper foil and a lithium foil or lithium alloy negative electrode; the positive plate is an aluminum foil coated with a lithium-rich material on two sides, and the lithium-rich material is one of lithium iron phosphate, an NCM ternary material, an NCA ternary material, lithium manganate or lithium cobaltate.
7. The quasi-solid battery of claim 1, wherein: the interface wetting additive comprises one or more of electrolyte formed by dissolving lithium metal salt in a solvent, molten salt electrolyte formed by compounding the lithium metal salt with other compounds or lithium metal salt alone, and ionic liquid electrolyte.
8. The method for preparing a composite pole piece of a quasi-solid battery without a diaphragm according to any one of claims 1 to 7, wherein the method comprises the following steps: the method comprises the following steps:
(1) mixing inorganic solid electrolyte powder, a dispersing agent, a binder and an organic solvent, and preparing inorganic solid electrolyte slurry through high-speed shearing dispersion or ball milling or sanding dispersion, wherein the stirring speed of the high-speed shearing dispersion is 800-1200 rpm; the rotating speed of the double planetary ball milling is 250-350 rpm; the sanding rotating speed is 1400-1800 rpm;
(2) compounding the inorganic solid electrolyte slurry on the surface of the negative plate by a coating method to form a coating layer, and drying the coating layer to obtain an inorganic coating;
(3) preparing organic polymer slurry by high-speed shearing dispersion or ball milling or sanding dispersion of an organic polymer, an acrylic resin binder and deionized water, wherein the stirring speed of the high-speed shearing dispersion is 800-1200 rpm; the rotating speed of the double planetary ball milling is 250-350 rpm; the sanding rotating speed is 1400-1800 rpm;
(4) and compounding the organic polymer slurry on the surface of the inorganic solid electrolyte layer by a coating method to form a coating layer, and drying the coating layer to obtain the coating.
9. The method for preparing the composite pole piece of the diaphragm-free quasi-solid battery according to claim 8, wherein the method comprises the following steps: the coating method comprises at least one of micro-concave coating, extrusion coating, transfer coating, screen printing, electrostatic spraying, atomized spraying, casting and 3D printing; when the organic polymer is oily slurry, spraying by at least one of electrostatic spraying and atomized spraying to obtain a spherical granular organic polymer layer; when the organic polymer is an aqueous slurry, coating by at least one of the coating methods described results in a spherical particulate organic polymer layer.
10. The method for preparing the composite pole piece of the diaphragm-free quasi-solid battery according to claim 8, wherein the method comprises the following steps: in the step (3), the organic polymer slurry can also be prepared by stirring and dissolving 10-30 parts of organic polymer in 70-90 parts of organic solvent.
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