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CN111653819A - Solid-state battery and preparation method thereof - Google Patents

Solid-state battery and preparation method thereof Download PDF

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Publication number
CN111653819A
CN111653819A CN202010526435.5A CN202010526435A CN111653819A CN 111653819 A CN111653819 A CN 111653819A CN 202010526435 A CN202010526435 A CN 202010526435A CN 111653819 A CN111653819 A CN 111653819A
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layer
electrolyte
solid
lithium
state battery
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Inventor
景茂祥
刘权垚
陈菲
陈浩
沈湘黔
鞠博伟
周倩
涂飞跃
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a solid-state battery which comprises a positive plate, an electrolyte layer, a modification layer and a negative plate, wherein the positive plate, the electrolyte layer, the modification layer and the negative plate are of an integrated structure. The preparation method comprises the following steps: flatly laying the positive plate on a heatable coating machine, coating a layer of electrolyte slurry on the positive plate, and heating to enable the electrolyte layer to be in a semi-solidification state; continuously coating a layer of modified slurry on the electrolyte layer in a semi-solidification state, and heating to ensure that the coating layer is basically solidified; and (3) covering a negative plate on the modified layer, applying vertical pressure, and heating to completely solidify the coating layer to obtain the solid-state battery. The solid-state lithium ion battery is of an integrated structure, the problem of interface combination of the anode and the electrolyte is solved in the assembling process, and meanwhile, the interface contact impedance of the electrolyte and the electrode is greatly reduced and the distribution uniformity of interface current is improved by selecting the modified layer, so that the growth of lithium dendrite is inhibited, and the cycle stability of the solid-state battery is improved.

Description

Solid-state battery and preparation method thereof
Technical Field
The invention belongs to the field of solid-state batteries, and particularly relates to a solid-state battery with an integrated structure and a preparation method thereof.
Background
A stable electrode/electrolyte interface is critical to the electrochemical performance of a solid state lithium battery. Solid electrolytes generally require a certain degree of rigidity, and the surfaces of electrodes (including positive and negative electrodes) are not flat, so that it is difficult to make ideal surface-to-surface contact between the electrodes and the electrolyte. In contrast, point-to-point contact ultimately results in higher interfacial resistance, thereby inhibiting lithium ion transport. In addition, the uneven charge distribution on the surface of the negative electrode promotes the growth of lithium dendrites during charge and discharge, and the high activity of metallic lithium tends to cause side reactions with the electrolyte at the interface. It is these interfacial problems that inhibit ion transport capabilities, resulting in decreased cell coulombic efficiency, poor power density, and faster capacity fade of solid-state batteries.
To ameliorate this technical problem, most research has focused on modifying the lithium negative electrode to inhibit the growth of lithium dendrites. For example, polyethylene oxide (PEO) is used as a protective layer to provide a dendrite-free coating of a lithium metal negative electrode, and poly (N-methyl-malonamide) is used to provide high temperature and high pressure performance; or a graphite soft interface is prepared on the surface of the lithium cathode, so that good ductility and compressibility are provided, but metal lithium is very active, the operation environment is harsh, and the metal lithium is easy to react with a solvent, so that the industrial application of preparing the graphite soft interface on the surface of the lithium cathode is a difficult problem. For the study of interface modification of positive electrode/electrolyte, a layer of ceramic solid electrolyte LATP is coated on the surface of NCM622 powder to reduce the space charge layer and alleviate polarization; or the LLZO nanowires are dispersed in polyethylene oxide (PEO) to form a composite solid electrolyte, which is melted at a high temperature and infiltrated into the positive electrode to form an integral structure, integrating the electrode/electrolyte, which effectively improves the physical contact area between the positive electrode and the electrolyte, thereby reducing the interface resistance. However, the modification research on the interface at present is basically to solve the interface problem between the positive electrode/electrolyte and the negative electrode/electrolyte respectively, and the preparation process is relatively complicated. There is a fresh research to solve the problem of the interface between the electrolyte and the positive and negative electrodes, for example, in CN108963328A, a transition layer containing a silicon oxide skeleton compound and an ionic liquid is used to enhance the interface bonding between the electrolyte and the positive and negative electrodes, but due to the introduction of the ionic liquid, the transition layer is actually a gel-state softening layer, and has no significant effect on the inhibition of lithium dendrites, and is implemented on the positive and negative electrodes respectively, which increases the complexity of the preparation process.
Disclosure of Invention
The technical problem to be solved by the present invention is to overcome the above mentioned disadvantages and drawbacks of the background art, and to provide a solid-state battery with an integrated structure and a method for manufacturing the same.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the solid-state battery comprises a positive plate, an electrolyte layer, a modification layer and a negative plate, wherein the positive plate, the electrolyte layer, the modification layer and the negative plate are of an integrated structure.
In the solid-state battery, preferably, the material of the modification layer is one or more selected from graphite, graphene oxide and carbon nanotubes. The carbon material is advantageous for improving the interface contact of the electrode/electrolyte and is capable of forming LiC with lithium ions6The method is favorable for promoting the current distribution of the interface and inhibiting lithium dendrites.
In the above solid-state battery, preferably, the material of the modification layer further includes LiF and AlF3One or two of them. Introduction of LiF and AlF into the modified layer3The fluoride and the carbon material cooperate with each other to further inhibit lithium dendrite and stabilize the performance of the battery.
In the above solid-state battery, preferably, the material of the electrolyte layer includes a polymer and a lithium salt; the mass ratio of the lithium salt to the polymer is 0.5: 10-3: 10.
In the solid-state battery, preferably, the polymer includes one or more of polyethylene oxide, polypropylene carbonate, polyvinylidene fluoride, poly (1, 3-dioxolane), and polyethylene glycol diglycidyl ether; the lithium salt comprises one or more of lithium perchlorate, lithium hexafluorophosphate, lithium difluorooxalate borate, lithium tetrafluoroborate and lithium bistrifluoromethylsulfonyl imide.
In the above solid-state battery, preferably, the positive plate includes one of a nickel-cobalt-manganese ternary positive plate, a lithium iron phosphate positive plate, a lithium cobaltate positive plate, and a sulfur positive plate; the negative electrode comprises one of a metal lithium electrode plate, a silicon-carbon electrode plate and a graphite electrode plate.
As a general inventive concept, the present invention also provides a method of manufacturing the above-described solid-state battery, including the steps of:
(1) flatly laying the positive plate on a heatable coating machine, coating a layer of electrolyte slurry on the positive plate, and heating to enable the electrolyte layer to be in a semi-solidification state;
(2) continuously coating a layer of modified slurry on the electrolyte layer in the semi-solidification state after the step (1), and heating to ensure that the coating layer is basically solidified;
(3) and (3) covering a negative plate on the modified layer obtained in the step (2), applying vertical pressure, and continuously heating to completely solidify the coating layer to obtain the solid-state battery.
In the preparation method, preferably, in the step (1) and the step (2), the heating temperature is 60-80 ℃, and the heating time is 5-10 minutes.
In the preparation method, preferably, in the step (3), the applied vertical pressure is 1-2 MPa; the temperature for continuous heating is 60-80 ℃, and the heating time is 15-25 min.
In the preparation method, preferably, the content of the electrolyte material in the electrolyte slurry is 20-100%; the modified slurry is an organic solvent solution with the material content of the modified layer accounting for 5-20%.
In the above preparation method, the organic solvent is preferably any one of N, N-dimethylformamide, anhydrous acetonitrile, acetone, N-methyl-2-pyrrolidone, and dimethyl sulfone.
Compared with the prior art, the invention has the advantages that:
(1) the solid lithium ion battery is of an integrated structure, not only solves the problem of interface combination of a positive electrode and an electrolyte in the assembly process, but also utilizes good ductility and proper rigidity between carbon material sheet layers and forms LiC by carbon materials, fluorides and lithium6The high-conductivity transition phase such as LiF and the like greatly reduces the interface contact resistance of the electrolyte and the electrode and improves the distribution uniformity of interface current, thereby inhibiting the growth of lithium dendrite and improving the cycle stability of the solid-state battery; compared with an in-situ polymerization method, the interface defect is easy to control, the modification of the cathode interface is more flexible, the in-situ polymerization method often causes a plurality of interface defects such as bubbles, holes and the like, particularly, an electrolyte/cathode interface modification layer can only be implemented on the cathode in advance, the flow is increased, and the contact effect of the solidified modification layer and the electrolyte is poor.
(2) The preparation method of the solid-state lithium ion battery with the integrated structure provided by the invention is directly carried out on the surface of the anode, the equipment and the preparation process are simple, the modification of an electrolyte/cathode interface is facilitated, the battery assembly process is simplified, and the preparation method is suitable for large-scale production.
(3) The solid lithium ion battery with the integrated structure is suitable for high-load electrodes, such as positive active substances which can reach 8mg/cm2The load capacity of the conventional solid-state battery electrode is only 2-3 mg/cm2The specific energy of the battery is greatly improved.
Drawings
Fig. 1 is a graph showing flexibility of an integrated structure of a cathode/electrolyte/modification layer prepared in example 1 of the present invention.
Fig. 2 is a surface SEM photograph of the cathode/electrolyte composite prepared in example 1 of the present invention.
Fig. 3 is an SEM photograph of the surface of the cathode/electrolyte/modified layer composite prepared in example 1 of the present invention.
Fig. 4 is a cross-sectional SEM photograph of the cathode/electrolyte/modified layer composite prepared in example 1 of the present invention.
Fig. 5 is an ac impedance diagram of the solid-state battery prepared in example 1 of the present invention.
Fig. 6 is a charge-discharge cycle curve diagram of the solid-state battery prepared in example 1 of the present invention.
Fig. 7 is a graph showing charge and discharge cycles of the solid-state battery prepared in example 5 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the solid-state battery comprises a positive plate, an electrolyte layer, a modification layer and a negative plate, wherein the positive plate, the electrolyte layer, the modification layer and the negative plate are of an integrated structure, the modification layer is made of graphite, the electrolyte layer is made of polymer polypropylene carbonate and lithium salt, and the mass ratio of the lithium salt to the polymer polypropylene carbonate is 1: 10; the positive plate is a commercial ternary NCM622 electrode plate; the negative electrode is a lithium metal electrode plate.
The method for manufacturing a solid-state battery according to the present embodiment includes the steps of:
(1) respectively preparing electrolyte slurry and modified slurry, wherein the electrolyte slurry is an N, N-dimethylformamide solution with the mass content of 20% of polypropylene carbonate, and the lithium salt is lithium bistrifluoromethylsulfonyl imide with the content of 10% of the polypropylene carbonate; the modified slurry is composed of acetone solution with graphite powder mass content of 10%;
(2) flatly laying a commercial ternary NCM622 electrode plate on a heatable coating machine, coating a layer of electrolyte slurry solution with the thickness of 200 microns by a scraper, and heating at 60 ℃ for 10 minutes until the electrolyte is in a semi-solidified state; continuously scraping a layer of graphite slurry with the thickness of 50 microns by using a scraper, and heating for 5 minutes at the temperature of 60 ℃; as shown in fig. 1, the solid-state battery of the integrated positive electrode/electrolyte/modification layer structure exhibited good flexibility;
(3) after the coating layer is basically solidified, covering a lithium sheet on the graphite layer, vertically pressurizing for 1 minute by using a tablet press under the pressure of 2MPa, continuously heating for 20 minutes at the temperature of 60 ℃ to obtain a solid-state battery with an integrated structure, and carrying out series tests after sealing by using an aluminum-plastic film.
Scanning electron microscope for observing the structure of the solid-state battery with the integral structure at different stages, wherein FIG. 2 is a surface SEM photo of the composite anode/electrolyte, FIG. 3 is a surface SEM photo of the composite anode/electrolyte/modified layer, and the original smooth surface of the modified layer is changed into a rough surface uniformly covered by graphite after being coated; fig. 4 is a cross-sectional SEM photograph of the cathode/electrolyte/modified layer after being compounded, and it can be clearly seen that the formed cathode, electrolyte and modified layer are tightly combined together.
The ac impedance analysis of the solid-state battery prepared in this example is shown in fig. 5, and it can be seen from fig. 5 that the impedance of the present invention is significantly lower than that of a conventional laminated battery in which the electrode, the electrolyte and the negative electrode are directly stacked.
The charge-discharge cycle curve of the solid-state battery prepared in the embodiment at the room temperature of 0.5C multiplying power is shown in fig. 6, and as can be seen from fig. 6, the initial capacity of the battery reaches 155mAh/g, and the retained capacity still reaches 142mAh/g after 100 cycles of circulation, so that the battery with the integrated structure shows stable circulation, the laminated battery has fast capacity attenuation and low coulombic efficiency.
Example 2:
the solid-state battery comprises a positive plate, an electrolyte layer, a modification layer and a negative plate, wherein the positive plate, the electrolyte layer, the modification layer and the negative plate are of an integrated structure, the modification layer is made of graphene oxide, the electrolyte layer is made of polymer polyvinylidene fluoride and lithium salt, and the mass ratio of the lithium salt to the polymer polyvinylidene fluoride is 3: 10; the positive plate is a lithium cobaltate electrode plate; the negative electrode is a graphite electrode plate.
The method for manufacturing a solid-state battery according to the present embodiment includes the steps of:
(1) respectively preparing electrolyte slurry and modified slurry, wherein the electrolyte slurry is an N-methyl-2 pyrrolidone solution with the mass content of polyvinylidene fluoride accounting for 50%, and lithium salt in the electrolyte slurry is lithium hexafluorophosphate accounting for 30% of polyvinylidene fluoride; the modified slurry is composed of an acetone solution with the mass content of graphene oxide accounting for 5%;
(2) spreading a lithium cobaltate electrode plate on a heatable coating machine, coating a layer of electrolyte slurry solution with the thickness of 300 microns by a scraper, and heating at 60 ℃ for 10 minutes to enable the electrolyte to be in a semi-solidified state; continuously carrying out blade coating on a layer of graphene oxide slurry with the thickness of 50 microns by using a scraper, and heating for 10 minutes at 80 ℃;
(3) and after the coating layer is basically solidified, covering a graphite cathode sheet on the graphene oxide layer, vertically pressurizing for 2 minutes by using a tablet press under the pressure of 1MPa, continuously heating for 20 minutes at the temperature of 80 ℃ to obtain the solid-state battery with the anode/electrolyte/modified layer/cathode in an integrated structure, and carrying out series tests after the aluminum-plastic film is sealed. The scanning electron microscope is used for observing the structures of the solid-state battery with the integrated structure at different stages, and the scanning electron microscope shows that the formed anode/electrolyte/modified layer are tightly combined together and have very good flexibility.
The initial capacity of the solid-state battery prepared by the embodiment at the room temperature under the multiplying power of 0.5C is tested to reach 145mAh/g, and after the solid-state battery is circulated for 100 circles, the retention capacity still reaches 120 mAh/g.
Example 3:
the solid-state battery comprises a positive plate, an electrolyte layer, a modification layer and a negative plate, wherein the positive plate, the electrolyte layer, the modification layer and the negative plate are of an integrated structure, the modification layer is made of graphite, the electrolyte layer is made of polymer polyethylene glycol diglycidyl ether and lithium salt, and the mass ratio of the lithium salt to the polyethylene glycol diglycidyl ether is 1.5: 8.5; the positive plate is a lithium iron phosphate electrode plate; the negative electrode is a silicon-carbon negative plate.
The method for manufacturing a solid-state battery according to the present embodiment includes the steps of:
(1) preparing electrolyte slurry and modified slurry, wherein the components of the electrolyte slurry are polyethylene glycol diglycidyl ether solution and lithium difluoro oxalate borate salt with the mass content of 15%; the modified slurry is composed of acetone solution with graphite powder mass content of 10%;
(2) spreading a conventional lithium iron phosphate electrode plate on a heatable coating machine, coating a layer of electrolyte slurry solution with the thickness of 100 microns by a scraper, and heating at 70 ℃ for 5 minutes to enable the electrolyte to be in a semi-solidified state; continuously scraping a layer of graphite slurry with the thickness of 20 microns by using a scraper, and heating for 5 minutes at the temperature of 60 ℃;
(3) after the coating layer is basically solidified, covering a silicon-carbon negative plate on the graphite layer, vertically pressurizing for 1 minute by a tablet press under the pressure of 2MPa, continuously heating for 20 minutes at the temperature of 60 ℃ to obtain a solid-state battery with an integrated structure of a positive electrode/electrolyte/modified layer/negative electrode, and carrying out series tests after the aluminum-plastic film is sealed.
The initial capacity of the solid-state battery prepared by the embodiment at the room temperature under the multiplying power of 0.5C reaches 167mAh/g, and after the solid-state battery is circulated for 200 circles, the retention capacity still reaches 143 mAh/g.
Example 4:
the solid-state battery comprises a positive plate, an electrolyte layer, a modification layer and a negative plate, wherein the positive plate, the electrolyte layer, the modification layer and the negative plate are of an integrated structure, the modification layer is made of graphite and/or LiF, the electrolyte layer is made of polymer poly (1, 3-dioxolane) and lithium salt, and the mass ratio of the lithium salt to the poly (1, 3-dioxolane) is 2: 8; the positive plate is a sulfur/C electrode plate; the negative electrode is a metal lithium sheet.
The method for manufacturing a solid-state battery according to the present embodiment includes the steps of:
(1) preparing electrolyte slurry and cathode modified layer slurry, wherein the electrolyte slurry comprises a poly (1, 3-dioxolane) solution, 5% of lithium tetrafluoroborate and 15% of lithium bistrifluoromethylsulfonyl imide in mass content; the components of the negative electrode modified layer slurry are acetone solution of a graphene oxide/LiF mixture (mass ratio is 1: 1) with the mass content of 15%.
(2) Spreading a commonly used sulfur/C electrode plate on a heatable coating machine, coating a layer of electrolyte slurry solution with the thickness of 150 microns by a scraper, heating for 6 minutes at 80 ℃, and semi-solidifying the electrolyte; continuously scraping a layer of graphene oxide/LiF mixture slurry with the thickness of 40 microns by using a scraper, and heating for 5 minutes at 80 ℃;
(3) and after the coating layer is basically solidified, covering a metal lithium sheet on the graphene oxide layer, vertically pressurizing for 2 minutes by using a tablet press under the pressure of 2MPa, continuously heating for 20 minutes at the temperature of 80 ℃ to obtain the solid-state battery with the integrated anode/electrolyte/modified layer/cathode, and carrying out series tests after the aluminum-plastic film is sealed.
The initial capacity of the solid-state battery prepared by the embodiment reaches 1007mAh/g under the room temperature and the multiplying power of 0.5C, and the retention capacity still reaches 865mAh/g after the circulation is performed for 100 circles.
Example 5:
the solid-state battery comprises a positive plate, an electrolyte layer, a modification layer and a negative plate, wherein the positive plate, the electrolyte layer, the modification layer and the negative plate are of an integrated structure, the modification layer is made of graphite, the electrolyte layer is made of polymers poly (1, 3-dioxolane) and lithium salt, and the mass ratio of the lithium salt to the poly (1, 3-dioxolane) is 2: 8; the positive plate is a sulfur/C electrode plate; the negative electrode is a metal lithium sheet.
The method for manufacturing a solid-state battery according to the present embodiment includes the steps of:
(1) preparing electrolyte slurry and cathode modified layer slurry, wherein the electrolyte slurry comprises a poly (1, 3-dioxolane) solution, 5% of lithium tetrafluoroborate and 15% of lithium bistrifluoromethylsulfonyl imide in mass content; the negative electrode modified layer slurry is composed of an acetone solution of graphene oxide with a mass content of 15%.
(2) Spreading a commonly used sulfur/C electrode plate on a heatable coating machine, coating a layer of electrolyte slurry solution with the thickness of 150 microns by a scraper, heating for 6 minutes at 80 ℃, and semi-solidifying the electrolyte; the graphene oxide mixture slurry was further coated with a 40 μm thick layer by a doctor blade and heated at 80 ℃ for 5 minutes.
(3) And after the coating layer is basically solidified, covering a metal lithium sheet on the graphene oxide layer, vertically pressurizing for 2 minutes by using a tablet press under the pressure of 2MPa, continuously heating for 20 minutes at the temperature of 80 ℃ to obtain the solid-state battery with the integrated anode/electrolyte/modified layer/cathode, and carrying out series tests after the aluminum-plastic film is sealed.
The solid-state cell prepared in this example was tested to achieve an initial capacity of 962mAh/g at 0.5C rate at room temperature, and a retained capacity of 829mAh/g after 100 cycles.
Example 6:
adopting a high-load lithium cobaltate positive electrode (5 mg/cm)2And 8.5mg/cm2) The conventional lithium cobaltate positive electrode (2 mg/cm) in example 2 was replaced with each other2) The procedure was the same as in example 2. The electrochemical performance of the solid-state battery was measured, and as shown in FIG. 7, the charge-discharge cycle curve shows that the solid-state battery (5 mg/cm)2Electrode) has initial capacity of 145mAh/g at room temperature under 0.5C multiplying power, and after circulating for 100 circles, the reserved capacity still reaches 120 mAh/g; solid-state battery (8.5 mg/cm)2Electrode) has initial capacity of 140mAh/g at room temperature under 0.5C multiplying power, and after 100 cycles of circulation, the retained capacity still reaches 106mAh/g, so that the integrated solid-state battery has stable circulation performance, and particularly, under a high-load electrode, the battery still shows good stability and circulation performance.

Claims (10)

1. The solid-state battery is characterized by comprising a positive plate, an electrolyte layer, a modification layer and a negative plate, wherein the positive plate, the electrolyte layer, the modification layer and the negative plate are of an integrated structure.
2. The solid-state battery according to claim 1, wherein the material of the modification layer is one or more selected from graphite, graphene oxide, and carbon nanotubes.
3. The solid-state battery according to claim 2, wherein the material of the modification layer further comprises LiF, AlF3One or two of them.
4. The solid-state battery according to claim 1, wherein the material of the electrolyte layer comprises a polymer and a lithium salt; the mass ratio of the lithium salt to the polymer is 0.5: 10-3: 10.
5. The solid state battery of claim 4, wherein the polymer comprises one or more of polyethylene oxide, polypropylene carbonate, polyvinylidene fluoride, poly (1, 3-dioxolane), polyethylene glycol diglycidyl ether; the lithium salt comprises one or more of lithium perchlorate, lithium hexafluorophosphate, lithium difluorooxalate borate, lithium tetrafluoroborate and lithium bistrifluoromethylsulfonyl imide.
6. The solid-state battery according to any one of claims 1 to 5, wherein the positive electrode sheet includes one of a nickel-cobalt-manganese ternary positive electrode sheet, a lithium iron phosphate positive electrode sheet, a lithium cobaltate positive electrode sheet, a sulfur positive electrode sheet; the negative electrode comprises one of a metal lithium electrode plate, a silicon-carbon electrode plate and a graphite electrode plate.
7. A method for producing a solid-state battery according to any one of claims 1 to 6, comprising the steps of:
(1) flatly laying the positive plate on a heatable coating machine, coating a layer of electrolyte slurry on the positive plate, and heating to enable the electrolyte layer to be in a semi-solidification state;
(2) continuously coating a layer of modified slurry on the electrolyte layer in the semi-solidification state after the step (1), and heating to ensure that the coating layer is basically solidified;
(3) and (3) covering a negative plate on the modified layer obtained in the step (2), applying vertical pressure, and continuously heating to completely solidify the coating layer to obtain the solid-state battery.
8. The method according to claim 7, wherein the heating temperature in the step (1) and the heating time in the step (2) are 60 to 80 ℃ and 5 to 10 minutes.
9. The method according to claim 7, wherein in the step (3), the vertical pressure is applied at 1 to 2 MPa; the temperature for continuous heating is 60-80 ℃, and the heating time is 15-25 min.
10. The method according to claim 7, wherein the electrolyte slurry contains 20 to 100% of the electrolyte material; the modified slurry is an organic solvent solution with the material content of the modified layer accounting for 5-20%.
CN202010526435.5A 2020-06-09 2020-06-09 Solid-state battery and preparation method thereof Pending CN111653819A (en)

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Application publication date: 20200911