CN111370754A - Preparation method of ultrathin electrolyte film and all-solid-state battery - Google Patents
Preparation method of ultrathin electrolyte film and all-solid-state battery Download PDFInfo
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- CN111370754A CN111370754A CN202010184171.XA CN202010184171A CN111370754A CN 111370754 A CN111370754 A CN 111370754A CN 202010184171 A CN202010184171 A CN 202010184171A CN 111370754 A CN111370754 A CN 111370754A
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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
- H01M10/056—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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- 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
- 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
Abstract
The invention discloses a preparation method of an ultrathin electrolyte film and an all-solid-state battery, which is characterized in that a lithium lanthanum zirconium oxygen electrolyte material, a lithium salt, a binder, a dispersant and a solvent are prepared into nano slurry by a high-energy ball milling method, and the nano slurry is prepared into a stable and compact ultrathin electrolyte film. In addition, matching anode and cathode materials are selected, and the ultrathin all-solid-state battery is assembled; the preparation method has the advantages of simple process, wide raw materials and low cost. The solid electrolyte film prepared by the method can reach 1 micron, the content of inorganic matters in the solid electrolyte film can reach 95 percent, and the all-solid-state battery has stable performance.
Description
Technical Field
The invention relates to the field of all-solid batteries, in particular to an ultrathin electrolyte film and a preparation method of an all-solid battery.
Background
Since the commercialization of lithium ion batteries, they have been widely used in various fields. However, the currently used organic electrolyte is a potential safety hazard of the lithium ion battery. The all-solid-state battery has the advantages of good safety, high energy density, good cycle performance and the like, and can fundamentally solve the safety problem of the liquid lithium ion battery. The composite solid electrolyte ensures good contact between the composite electrolyte and an electrode material on the basis of the flexibility of the organic electrolyte. In addition, by adding the inorganic material, not only can the ionic conductivity be improved, but also the mechanical strength of the electrolyte material can be enhanced. The composite electrolyte is the electrolyte which is most widely applied at present. However, the organic-inorganic composite electrolyte takes a large amount of organic matters as a substrate, and is not as good as a pure inorganic electrolyte in terms of safety performance; therefore, the content of the inorganic component in the composite electrolyte material is improved, and the safety performance of the battery is obviously improved.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to prepare a composite solid electrolyte film having a high inorganic component content by a simple process and to assemble an all-solid battery. The preparation method has the characteristics of simple raw materials, low energy consumption, stable property, simple steps, high repetition rate and the like.
The technical scheme adopted by the invention is as follows:
a preparation method of an ultrathin electrolyte film comprises the following steps:
1) adding 1 part by weight of lithium lanthanum zirconium oxygen into 5-100 parts by weight of a solvent, stirring for 1-12 hours, transferring to a zirconium oxide ball milling tank, and carrying out ball milling to obtain nano lithium lanthanum zirconium oxygen slurry; then adding 0.5-2 parts by weight of lithium salt, 0.01-0.2 part by weight of dispersant and 0.01-0.2 part by weight of binder, and adjusting the viscosity of the slurry;
2) and preparing the electrolyte film layer on the surface of the selected electrode material by using a film forming method by using the prepared slurry, wherein the concentration and the dosage of the slurry are required to be controlled so as to adjust the wetting angle between a solid interface and a liquid interface.
In the above technical scheme, the solvent in step 1) is a mixed solution of N-methylpyrrolidone (NMP), Propylene Carbonate (PC), Ethylene Carbonate (EC), and dimethyl carbonate (DMC), and the weight ratio of the components is NMP: PC: EC: the DMC is 50-100: 1-35: 1-25: 1-20.
The dispersing agent in the step 1) is Sodium Dodecyl Benzene Sulfonate (SDBS), Cetyl Trimethyl Ammonium Bromide (CTAB), EO-PO type polyether (F127) and polyoxyethylene-polyoxypropylene-polyoxyethylene (P123), and the mass ratio of the dispersing agent to the dispersing agent is SDBS: CTAB: f127: p123 is 1-25: 1-30: 1-95: 1-20.
The viscosity of the slurry obtained in the step 1) is 0.1-50 cP at room temperature; the viscosity is 0.01-30 cP at 100 ℃.
And 3) when the electrode material selected in the step 2) is a lithium metal cathode, controlling the interface wetting angle between the slurry and the lithium metal cathode to be 0.01-15 degrees, and when the electrode material selected is a mixed anode material, controlling the interface wetting angle between the slurry and the mixed anode material to be 0.01-30 degrees.
The film forming method in the step 2) comprises: casting or screen printing or 3D printing.
A preparation method of an all-solid-state thin film battery is characterized in that the obtained electrolyte thin film layer sample is naturally cooled to room temperature after being subjected to heat treatment, and another electrode material which can form a positive electrode and a negative electrode with the electrode material obtained in the step 2) is selected and assembled into the all-solid-state thin film battery.
In the present invention, the above-mentioned preferred conditions can be arbitrarily combined on the basis of common knowledge in the field, so as to obtain each preferred embodiment of the present invention.
The method of the invention is that the lithium lanthanum zirconium oxygen electrolyte material, lithium salt, adhesive, dispersant and solvent are prepared into nano slurry by a high-energy ball milling method, and then the nano slurry is prepared into a stable and compact ultrathin electrolyte film layer. In addition, matching anode and cathode materials are selected, and the ultrathin all-solid-state battery is assembled; the preparation method has the advantages of simple process, wide raw materials and low cost. The solid electrolyte film prepared by the method can reach 1 micron, the content of inorganic matters in the solid electrolyte film can reach 95 percent, and the all-solid-state battery has stable performance.
The invention has the beneficial effects that:
the preparation method of the ultrathin electrolyte film and the all-solid-state battery mainly has the following advantages: 1. the method has the advantages of no need of a die, convenient operation 2, natural forming, no need of pressure 3 in the preparation process, free control of film thickness 4, adjustable slurry concentration and viscosity and suitability for various electrode materials. 5. The raw materials and the reagents are commercially available, and the method is convenient and simple 6. each test is controllable and has high repeatability.
Drawings
Fig. 1 is an external view of a nano-electrolyte slurry;
FIG. 2 is the cycle performance of an LCO/Li all-solid-state thin film battery;
FIG. 3 is the cycle performance of an LFPO/Li all-solid-state thin film battery;
FIG. 4 is the cycling performance of an NMC811/Li all-solid-state thin film battery.
Detailed Description
While the following is a description of the preferred embodiment of the present invention, it should be noted that numerous modifications and adaptations could be made by those skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Example 1
Taking 1 part by weight of lithium lanthanum zirconium oxide, 10 parts by weight of solvent (NMP: PC: EC: DMC: 5: 1: 1: 3), 0.5 part by weight of LiPF6 as lithium salt, 0.1 part by weight of PVDF as binder, 0.1 part by weight of dispersant (SDBS: CTAB: F127: P123: 2: 3: 1: 2), ball-milling for 1h at the rotating speed of 800r/min, and obtaining slurry with the viscosity of 1.3cP at room temperature. The slurry is shown in figure 1 (a); selecting a lithium cobaltate composite positive electrode plate, diluting by 2 times, controlling the wetting angle to be 13 degrees, and annealing for 12 hours at 200 ℃ after silk-screen printing to obtain the ultrathin electrolyte film. And selecting a lithium metal negative electrode, and assembling the thin film battery, which is marked as an LCO/Li all-solid-state thin film battery. The cycling effect is shown in figure 2.
Example 2
Taking 1 part by weight of lithium lanthanum zirconium oxide, 10 parts by weight of solvent (NMP: PC: EC: DMC: 8: 0.5: 1: 0.5), 0.5 part by weight of LiTFSi as lithium salt, 0.1 part by weight of SPEEK-PSI-Li as binder and 0.1 part by weight of dispersant (SDBS: CTAB: F127: P123: 1: 3: 5: 5), ball-milling for 2h at the rotating speed of 1200r/min to obtain slurry with the viscosity of 1.1cP at room temperature. And selecting a metal lithium sheet as a cathode, diluting by 5 times, controlling the wetting angle to be 9 degrees, and annealing at 120 ℃ for 6 hours after screen printing to obtain the ultrathin electrolyte film. And selecting a lithium cobaltate positive electrode material, and assembling the thin film battery.
Example 3
Taking 1 weight part of lithium lanthanum zirconium oxide, 10 weight parts of solvent (NMP: PC: EC: DMC: 10: 0.1: 0.1: 0.1), 0.3 weight part of LiBOB as lithium salt, 0.1 weight part of SPEEK-PSI-Li as binder, 0.2 weight part of dispersant (SDBS: CTAB: F127: P123: 0.5: 10: 0.2), ball-milling for 1h at the rotating speed of 1500r/min, and obtaining slurry with the viscosity of 2.5cP at room temperature. Selecting a lithium iron phosphate composite positive electrode plate, diluting by 10 times, controlling the wetting angle to be 10 degrees, and annealing at 200 ℃ for 4 hours after 3D printing to obtain the ultrathin electrolyte film. And selecting a lithium metal negative electrode, and assembling the thin film battery which is marked as an LFPO/Li all-solid-state thin film battery. The cycling effect is shown in figure 3.
Example 4
1 part by weight of lithium lanthanum zirconium oxide, 10 parts by weight of solvent (NMP: PC: EC: DMC ═ 1: 10: 1: 3), 0.5 part by weight of LiPF6As the lithium salt, 0.1 part by weight of PVDF as a binder, 0.1 part by weight of a dispersant (SDBS: CTAB: F127: P123 ═ 5: 3: 1: 5) were ball-milled for 4 hours at a rotation speed of 1200r/min to obtain a slurry having a viscosity of 1.5cP at room temperature. The slurry is shown in FIG. 1 (b); selecting a lithium iron phosphate composite anode electrode plate, diluting by 2 times, controlling the wetting angle to be 10 degrees, preparing the lithium iron phosphate composite anode electrode plate on the anode electrode plate by a tape casting method, and annealing for 12 hours at 200 ℃ to obtain the ultrathin electrolyte film. And selecting a lithium metal negative electrode, and assembling the thin film battery.
Example 5
1 part by weight of lithium lanthanum zirconium oxide, 10 parts by weight of solvent (NMP: PC: EC: DMC ═ 1: 10: 1: 3), 0.5 part by weight of LiPF6As the lithium salt, 0.1 part by weight of PVDF as a binder, 0.1 part by weight of a dispersant (SDBS: CTAB: F127: P123 ═ 5: 3: 1: 5) were ball-milled for 3 hours at a rotation speed of 1500r/min to obtain a slurry having a viscosity of 1.5cP at room temperature. Selecting a metal lithium cathode electrode slice, diluting by 2 times, controlling the wetting angle to be 10 degrees, preparing the metal lithium cathode electrode slice on an anode slice by a tape casting method, and annealing for 12 hours at 200 ℃ to obtain the ultrathin electrolyte film. And selecting a lithium metal negative electrode, and assembling the thin film battery.
Example 6
Taking 1 weight part of lithium lanthanum zirconium oxide, 10 weight parts of solvent (NMP: PC: EC: DMC: 10: 1: 1: 1), 0.5 weight part of LiTFSi as lithium salt, 0.1 weight part of PVDF as binder, 0.1 weight part of dispersant (SDBS: CTAB: F127: P123: 2: 3: 1: 2), ball-milling for 2h at the rotating speed of 1500r/min, and obtaining slurry with the viscosity of 0.9cP at room temperature. Selecting a nickel-cobalt-manganese 811 composite anode electrode slice, diluting by 5 times, controlling the wetting angle to be 13 degrees, preparing the cathode electrode slice by a tape casting method, and annealing at 150 ℃ for 12 hours to obtain the ultrathin electrolyte film. And selecting a lithium metal negative electrode, and assembling a thin film battery, which is marked as an NMC811/Li all-solid-state thin film battery. The cycling effect is shown in figure 4.
Claims (7)
1. A preparation method of an ultrathin electrolyte film is characterized by comprising the following steps:
1) adding 1 part by weight of lithium lanthanum zirconium oxygen into 5-100 parts by weight of a solvent, stirring for 1-12 hours, transferring to a zirconium oxide ball milling tank, and carrying out ball milling to obtain nano lithium lanthanum zirconium oxygen slurry; then adding 0.5-2 parts by weight of lithium salt, 0.01-0.2 part by weight of dispersant and 0.01-0.2 part by weight of binder, and adjusting the viscosity of the slurry;
2) and preparing the electrolyte film layer on the surface of the selected electrode material by using a film forming method by using the prepared slurry, wherein the concentration and the dosage of the slurry are required to be controlled so as to adjust the wetting angle between a solid interface and a liquid interface.
2. The method for preparing an ultra-thin electrolyte membrane according to claim 1, wherein the solvent in step 1) is a mixed solution of N-methylpyrrolidone (NMP), Propylene Carbonate (PC), Ethylene Carbonate (EC), and dimethyl carbonate (DMC) in a weight ratio of NMP: PC: EC: the DMC is 50-100: 1-35: 1-25: 1-20.
3. The method of preparing an ultra-thin electrolyte membrane according to claim 1, wherein the dispersant in step 1) is Sodium Dodecylbenzenesulfonate (SDBS), cetyltrimethylammonium bromide (CTAB), EO-PO type polyether (F127), and polyoxyethylene-polyoxypropylene-polyoxyethylene (P123) in a mass ratio of SDBS: CTAB: f127: p123 is 1-25: 1-30: 1-95: 1-20.
4. The method for preparing an ultrathin electrolyte film according to claim 1, characterized in that the viscosity of the slurry of the step 1) is 0.1 to 50cP at room temperature; the viscosity is 0.01-30 cP at 100 ℃.
5. The method for preparing an ultrathin electrolyte film according to claim 1, wherein the wetting angle of the interface between the slurry and the metallic lithium negative electrode is controlled to be 0.01 to 15 ° when the electrode material selected in step 2) is a metallic lithium negative electrode, and the wetting angle of the interface between the slurry and the mixed positive electrode material is controlled to be 0.01 to 30 ° when the electrode material selected is a mixed positive electrode material.
6. The method for producing an ultrathin electrolyte thin film according to claim 1, wherein the film formation method in step 2) is: casting or screen printing or 3D printing.
7. A preparation method of an all-solid-state thin film battery is characterized in that a sample obtained in the step 1 is subjected to heat treatment and then naturally cooled to room temperature, and another electrode material which can form a positive electrode and a negative electrode with the electrode material in the step 2) is selected and assembled into the all-solid-state thin film battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113363556A (en) * | 2021-05-31 | 2021-09-07 | 天能帅福得能源股份有限公司 | Novel all-solid-state lithium ion battery |
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| US20180342764A1 (en) * | 2013-10-07 | 2018-11-29 | Quantumscape Corporation | Garnet materials for li secondary batteries and methods of making and using garnet materials |
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2020
- 2020-03-16 CN CN202010184171.XA patent/CN111370754A/en not_active Withdrawn
Patent Citations (4)
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| CN105745778A (en) * | 2013-08-29 | 2016-07-06 | 联邦科学和工业研究机构 | Lithium-sulfur electric current producing cell |
| US20180342764A1 (en) * | 2013-10-07 | 2018-11-29 | Quantumscape Corporation | Garnet materials for li secondary batteries and methods of making and using garnet materials |
| CN105914396A (en) * | 2016-06-01 | 2016-08-31 | 浙江大学 | Preparation method of ultrathin nano-lithium lanthanum zirconium oxygen all-solid-state electrolyte layer |
| CN108448169A (en) * | 2018-03-15 | 2018-08-24 | 清陶（昆山）能源发展有限公司 | A kind of inorganic-organic hybrid solid electrolyte membrane and its processing technology |
Non-Patent Citations (1)
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| 严旭丰: "超薄锂镧锆氧固体电解质薄膜的制备与应用", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113363556A (en) * | 2021-05-31 | 2021-09-07 | 天能帅福得能源股份有限公司 | Novel all-solid-state lithium ion battery |
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Application publication date: 20200703 |