CN117577952A - Solid state battery and method of manufacture - Google Patents
Solid state battery and method of manufacture Download PDFInfo
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- CN117577952A CN117577952A CN202311823187.0A CN202311823187A CN117577952A CN 117577952 A CN117577952 A CN 117577952A CN 202311823187 A CN202311823187 A CN 202311823187A CN 117577952 A CN117577952 A CN 117577952A
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- 238000000034 method Methods 0.000 title claims description 25
- 239000007787 solid Substances 0.000 title claims description 19
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 57
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000002002 slurry Substances 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 56
- 238000007639 printing Methods 0.000 claims description 43
- 239000011230 binding agent Substances 0.000 claims description 21
- 238000010146 3D printing Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000005518 polymer electrolyte Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 5
- 210000001161 mammalian embryo Anatomy 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 4
- 229910021483 silicon-carbon alloy Inorganic materials 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
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- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002001 electrolyte material Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
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- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0404—Machines for assembling 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
- H01M10/052—Li-accumulators
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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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
-
- 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
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- General Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention belongs to the technical field of solid-state batteries, and relates to a solid-state battery and a manufacturing method thereof, wherein the solid-state battery comprises an anode current collector, a cathode current collector and a composite 3D structure; the composite 3D structure includes a positive electrode, a negative electrode, and a solid electrolyte; the solid electrolyte is arranged between the positive electrode current collector and the negative electrode current collector; the positive electrode is arranged on the positive electrode current collector and extends into the solid electrolyte along the direction from the positive electrode current collector to the negative electrode current collector; the negative electrode is disposed on the negative electrode current collector and extends into the solid electrolyte in a direction from the negative electrode current collector to the positive electrode current collector. The invention provides a solid-state battery and a manufacturing method thereof, which can effectively improve the multiplying power performance and the power density of the solid-state battery, improve the energy density of the solid-state battery and improve the cycle performance of the battery.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, relates to a solid-state battery and a manufacturing method thereof, and particularly relates to a polymer solid-state battery with a composite 3D structure and a manufacturing method thereof.
Background
The sandwich structure is the most widely used structure in the solid-state battery, the positive electrode, the solid-state electrolyte and the negative electrode layer are sequentially stacked and assembled together, and the battery with the structure has the advantages that the preparation method is simple and easy for mass production, but the interface contact between the positive electrode and the negative electrode of the battery and the solid-state electrolyte is two-dimensional contact, the contact form is single, the electron/ion transmission path is less, and the high-surface-capacity solid-state battery is difficult to prepare; in addition, the volume expansion of the active material during the charge and discharge of the battery can damage interface contact, thereby deteriorating the cycle performance of the battery. Solid-state lithium batteries with low tortuosity in 3D structures are an effective way to promote charge transport kinetics and improve battery rate performance due to the ability to increase electrode/solid electrolyte interface contact and provide direct electron/ion transport paths and three-dimensional diffusion channels inside the battery. However, the main methods for constructing the solid-state battery in the structure form at present are an ice template method, a wood template method, a magnetic auxiliary template method and the like, so that the preparation process is complex, the filling effect of the electrolyte in the electrode material gap is difficult to ensure, and the 3D structure design with low tortuosity is single due to the process limitation, so that the large-scale application and development of the solid-state battery in the structure form are hindered.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides a solid-state battery and a manufacturing method thereof, which can effectively improve the multiplying power performance and the power density of the solid-state battery, improve the energy density of the solid-state battery and improve the cycle performance of the battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a solid-state battery characterized in that: the solid-state battery comprises a positive current collector, a negative current collector and a composite 3D structure; the composite 3D structure includes a positive electrode, a negative electrode, and a solid electrolyte; the solid electrolyte is arranged between the positive electrode current collector and the negative electrode current collector; the positive electrode is arranged on the positive electrode current collector and extends into the solid electrolyte along the direction from the positive electrode current collector to the negative electrode current collector; the negative electrode is arranged on the negative electrode current collector and extends into the solid electrolyte along the direction from the negative electrode current collector to the positive electrode current collector.
The positive electrodes and the negative electrodes are all multiple, and the positive electrodes and the negative electrodes are arranged in a staggered and parallel mode.
The distance between the positive electrode and the negative electrode is 10-20 μm.
The length of the positive electrode extending from the positive electrode current collector into the solid electrolyte is 1.0-3.5 mm; the length of the negative electrode extending from the negative electrode current collector into the solid electrolyte is 1.5-4.0 mm.
The positive electrode and the negative electrode are of three-period minimum curved surface structures, in particular to three-period minimum curved surface structures which are constructed by a plurality of identical structural units after repetition; the size of the structural unit is 0.1-0.5 mm, and the relative density is 30-50%.
The thickness of the positive electrode current collector and the negative electrode current collector is 10-20 mu m; the total thickness of the solid-state battery is 1.7 to 4.2mm.
A method for producing a solid-state battery as described above, characterized by: the method comprises the following steps:
1) Preparing raw materials; the raw materials comprise a positive electrode active material, a conductive agent, a negative electrode active material, a solid electrolyte material and a binder;
2) Configuring printable slurry according to the raw materials prepared in step 1); the printable slurry comprises positive electrode printing slurry, negative electrode printing slurry and solid electrolyte slurry;
3) Printing the printable slurry obtained in the step 2) based on a multi-material 3D printing mode to form a composite 3D structure;
4) And 3) respectively assembling an anode current collector and a cathode current collector on the 3D structure prepared in the step 3), and packaging the battery after rolling treatment to obtain the solid-state battery.
In the step 1), the positive electrode active material is lithium iron phosphate or manganateOne or more of lithium, lithium cobaltate, lithium titanate, and ternary materials; the conductive agent is one or more of super, conductive carbon black, acetylene black, graphene and carbon nano tubes; the negative electrode active material is one or more of graphite, carbon black, graphene, silicon-carbon alloy, metallic lithium and alloy thereof; the binder comprises polyvinylpyrrolidone (PVP) and polyvinylidene fluoride (PVDF); the solid electrolyte material is polymer electrolyte and lithium salt; the polymer electrolyte is polyethylene oxide (PEO) and Polyacrylonitrile (PAN), and the lithium salt is LiTFSI or LiClO 4 And LiBF 4 ；
In the step 2), the positive electrode printing slurry comprises a positive electrode active material, a conductive agent and a binder; the negative electrode printing slurry comprises a negative electrode active material and a binder; the solid electrolyte slurry includes an electrolyte material and a binder; the printable slurry is configured in the following way: the raw materials used for printing paste are mixed according to the required proportion, and the printing paste with proper rheological property and stable property is obtained after mechanical stirring and even stirring.
The specific implementation manner of the step 3) is as follows:
3.1 Respectively placing the printable slurry prepared in the step 2) into different feeding devices of the multi-material 3D printing equipment;
3.2 Obtaining a blank composed of a positive electrode, a solid electrolyte and a negative electrode based on a multi-material 3D printing mode;
3.3 Cleaning the embryo body prepared in the step 3.2) to obtain a composite 3D structure consisting of a positive electrode, a solid electrolyte and a negative electrode;
in the step 4), the positive current collector is aluminum foil; the negative electrode current collector is a copper foil.
A solid-state battery prepared based on the method as described above.
The invention has the advantages that:
the invention provides a compound 3D structure solid-state battery and a manufacturing method thereof, firstly, a compound 3D structure solid-state battery is constructed, and the internal structure is characterized in that positive and negative poles respectively extend along the direction of a current collector on the surface of the current collector and are in cross arrangement in the battery, and solid electrolyte is filled between the positive and negative poles; secondly, an integrated preparation process for realizing the polymer solid-state battery by using the multi-material 3D printing equipment is provided. Specifically, the invention has the following advantages:
1. the design of the vertical 3D channels with low tortuosity and the regular connecting pore canal with a very small curved surface structure provides a three-dimensional rapid substance transmission channel in the battery, increases the ion/electron transmission rate and effectively improves the multiplying power performance and the power density of the solid-state battery.
2. The composite 3D structure design greatly increases the contact area of the electrode-solid electrolyte interface and the number of active sites (the contact area of the electrode material and the electrolyte is increased), effectively improves the utilization rate of the electrode active material, avoids the reaction polarization caused by the charge transport and the reaction kinetic difference in the traditional thick electrode design, and further improves the energy density of the solid battery.
3. The electrode structure design of the three-period minimum curved surface can improve the adaptability of the electrode material to volume change in the charge and discharge process, and can inhibit the growth of lithium dendrite when being used for a lithium metal negative electrode, so that the interface stress and the lithium dendrite problem are improved, and the cycle performance of the battery is improved.
4. The advantages of material distribution and structure manufacturing of the additive manufacturing technology are fully exerted, the manufacturing cost is reduced, the steps of the preparation process are simple, and large-scale mass production is facilitated; the multi-material printing technology helps to realize the possibility of preparing the battery cells with various structures, and improves the overall performance of the battery; the battery shape can be customized, the design freedom degree is high, and the whole battery shape can be designed according to the requirements of different application scenes, and the battery shape is not limited to round and square batteries.
Drawings
Fig. 1 is a schematic cross-sectional structure view of a composite 3D structure solid-state battery provided by the present invention;
FIG. 2 is a schematic diagram of a porous electrode structure and pore distribution thereof according to the present invention;
wherein:
1-positive electrode current collector; 2-composite 3D structure; 3-negative electrode current collector; 4-positive electrode; 5-negative electrode; 6-solid state electrolyte; 7-an all-solid-state battery; 8-porous electrode; 9-electrode internal channels (filled with solid electrolyte).
Detailed Description
Referring to fig. 1, the present invention provides a solid-state battery including a positive electrode current collector 1, a negative electrode current collector 3, and a composite 3D structure 2; the composite 3D structure 2 comprises a positive electrode 4, a negative electrode 5 and a solid electrolyte 6; a solid electrolyte 6 is interposed between the positive electrode current collector 1 and the negative electrode current collector 3; the positive electrode 4 is arranged on the positive electrode current collector 1 and extends into the solid electrolyte 6 along the direction from the positive electrode current collector 1 to the negative electrode current collector 3; the negative electrode 5 is arranged on the negative electrode current collector 3 and extends into the solid electrolyte 6 along the direction from the negative electrode current collector 3 to the positive electrode current collector 1; the positive electrode 4 and the negative electrode 5 are both three-period extremely small curved structures.
The solid-state battery provided by the invention is a porous design which is formed by adding the structure of the electrode on the basis of the low-tortuosity battery structure design. The positive electrodes 4 and the negative electrodes 5 are all plural, and the positive electrodes 4 and the negative electrodes 5 are arranged in a staggered and parallel manner. Illustratively, the positive electrode is vertically arranged on the surface of the positive electrode current collector 1, and the negative electrode is vertically arranged on the surface of the negative electrode current collector 3. Meanwhile, the positive electrode 4 and the negative electrode 5 are in crossed arrangement and extend in opposite directions in the solid electrolyte 6, and a certain distance is reserved between the electrode posts, and the distance between the positive electrode 4 and the negative electrode 5 is 10-20 μm by way of example. The length of the positive electrode 4 extending from the positive electrode current collector 1 into the solid electrolyte 6 is 1.0-3.5 mm; the length of the anode 5 extending from the anode current collector 3 into the solid electrolyte 6 is 1.5-4.0 mm. The positive electrode 4 and the negative electrode 5 are three-period minimum curved surface structures which are formed by repeating a plurality of identical structural units, and as shown in fig. 2, the curved surface structures are formed by porous electrodes 8, and electrode internal pore channels 9 in the porous electrodes 8 are filled with solid electrolyte; the size of the structural unit is 0.1-0.5 mm, and the relative density is 30-50%.
The thickness of the positive electrode current collector 1 and the negative electrode current collector 3 is 10-20 mu m; the total thickness of the solid-state battery is 1.7 to 4.2mm.
The present invention also provides a method for producing a solid-state battery as described above, characterized by: the method comprises the following steps:
1) Preparing raw materials; the raw materials comprisePositive electrode active material, conductive agent, negative electrode active material, solid electrolyte material and binder; the positive active material is one or more of lithium iron phosphate, lithium manganate, lithium cobaltate, lithium titanate and ternary materials; the conductive agent is one or more of super p, conductive carbon black, acetylene black, graphene and carbon nano tubes; the negative electrode active material is one or more of graphite, carbon black, graphene, silicon carbon alloy, metallic lithium and alloys thereof; the binder is any one or combination of polyvinylpyrrolidone (PVP) and polyvinylidene fluoride (PVDF); the solid electrolyte material is polymer electrolyte and lithium salt, and the molar ratio of the polymer electrolyte to the lithium salt is 15:1-20:1; the polymer electrolyte is any one or combination of polyethylene oxide (PEO) and Polyacrylonitrile (PAN), and the lithium salt is LiTFSI, liClO 4 And LiBF 4 Any one or a combination thereof;
2) Configuring printable slurry according to the raw materials prepared in step 1); printable slurries include positive printing slurries, negative printing slurries, and solid electrolyte slurries; the positive printing slurry comprises a positive active material, a conductive agent and a binder; the negative electrode printing slurry comprises a negative electrode active material and a binder; the solid electrolyte slurry comprises a solid electrolyte material and a binder; the printable slurry is configured in the following manner: the raw materials used for printing slurry are mixed according to the required proportion, mechanical stirring is carried out, the printing slurry with proper rheological property and stable property is obtained after uniform stirring, and the printing can be normally carried out with proper rheological property by way of example, and the stable property means that all components in the slurry are uniformly distributed and have no precipitation or layering phenomenon.
3) Printing the printable slurry obtained in the step 2) based on a multi-material 3D printing mode to form a composite 3D structure 2, specifically:
3.1 Respectively placing the printable slurries prepared in the step 2) into different feeding devices of the multi-material 3D printing equipment, and establishing a corresponding relation between forming materials and the numbers of the feeding devices in a control system of the multi-material printing equipment; a cleaning device containing ethanol solution is arranged on one workbench of the multi-material 3D printing equipment and is used for cleaning parts in the forming process. By way of example, the multi-material 3D printing apparatus may be an additive manufacturing apparatus based on photo-curing and material extrusion.
3.2 In the multi-material 3D printing forming process, the industrial control system extracts information of each material distribution area of each layer of the multi-material part according to the slicing file, and realizes multi-material nested printing forming by converting feeding devices filled with different printing pastes into a working area, so as to finally obtain a blank body composed of an anode, a solid electrolyte and a cathode;
3.3 Cleaning the embryo body prepared in the step 3.2) to obtain a composite 3D structure 2 consisting of a positive electrode, a solid electrolyte and a negative electrode;
4) Respectively assembling an anode current collector 1 and a cathode current collector 3 on the 3D structure 2 prepared in the step 3), enhancing the binding force of each part of the battery through rolling treatment, and then packaging the battery to obtain a solid-state battery 7, wherein the anode current collector 1 is an aluminum foil; the negative electrode current collector 3 is copper foil.
The solid-state battery 7 finally prepared based on the preparation method provided by the invention.
The method of manufacturing a solid-state battery according to the present invention will be described in detail with reference to several preferred embodiments.
Example 1 preparation of PEO-based Polymer solid State batteries
In this example, a PEO-based polymer solid state battery consisted of a positive current collector, a composite 3D structure "positive-solid electrolyte-negative", a negative current collector. Wherein the thickness of the solid-state battery is 1.7mm, the thickness of the positive electrode current collector (aluminum foil) is 16 mu m, and the thickness of the negative electrode current collector (copper foil) is 10 mu m; the positive pole and the negative pole are of a three-period minimum curved surface structure Gyroid, the size of a structural unit is 0.2mm, and the relative density is 35%; meanwhile, the extension length of the positive electrode post along the direction vertical to the current collector is 1.2mm, and the extension length of the negative electrode post along the direction vertical to the current collector is 1.5mm; the positive and negative electrode spacing was 12 μm in the case of the cross arrangement.
In this example, the positive electrode active material was lithium iron phosphate, the conductive agent was conductive carbon black, the binder was polyvinylpyrrolidone (PVP), and dispersion was performed using nitrogen-methylpyrrolidone (NMP); the negative electrode active material is silicon-carbon alloy, the binder is hydroxyethyl cellulose (CMC), and simultaneously acetone solution is selected for dispersion; the solid electrolyte materials are polyethylene oxide (PEO) and LiTFSI.
The preparation process of the PEO-based polymer solid-state battery provided by the example comprises the following steps:
1) Preparing positive electrode printing slurry, negative electrode printing slurry and solid electrolyte slurry, wherein the specific steps comprise:
1.1 Raw materials required for preparing the printable slurry, including a positive electrode active material, a conductive agent, a negative electrode active material, a solid electrolyte material, and a binder.
Treatment of solid electrolyte material: placing polyethylene oxide into a vacuum drying oven with the temperature of 40 ℃ for drying treatment for 12 hours; simultaneously, liTFSI is placed in a vacuum drying oven with the temperature of 100 ℃ for drying treatment for 12 hours;
electrode material treatment: the lithium iron phosphate and the conductive carbon material with a certain proportion are weighed and mixed, and then are ground for 18 hours in a ball mill at the speed of 250 r/min.
1.2 Using the material after pretreatment in step 1.1) to formulate a printable slurry: the components are mixed according to the required proportion and mechanically stirred, and finally the printing slurry with proper rheological property and stable property is obtained. The solid phase part of the positive printing slurry comprises 85% of lithium iron phosphate, 10% of conductive carbon black and 5% of polyvinylpyrrolidone (PVP) according to mass fraction, wherein the mass ratio of nitrogen-methyl pyrrolidone (NMP) to the solid phase is 1:5, a step of; the solid phase part of the negative electrode printing slurry comprises 80% of artificial graphite, 20% of hydroxyethyl cellulose and an ethanol solution, wherein the mass ratio of the ethanol solution to the solid phase is 1:7, preparing a base material; the molar ratio of polyethylene oxide to LiTFSI in the solid electrolyte slurry was 15:1.
2) The multi-material 3D printing equipment is used for forming the anode-solid electrolyte-cathode, and the specific implementation forms are as follows:
2.1 Respectively placing the printable slurries prepared in the step 1) in different feeding devices, and establishing a corresponding relation between forming materials and the numbers of the feeding devices in a control system of the multi-material printing equipment; a cleaning device containing ethanol solution is arranged on one workbench of the multi-material 3D printing equipment and is used for cleaning parts in the forming process.
2.2 In the multi-material 3D printing forming process, the industrial control system extracts information of each material distribution area of each layer of the multi-material part according to the slicing file, and realizes the multi-material nested printing process by converting feeding devices filled with different printing pastes into a working area, so as to finally obtain a composite 3D structure anode-solid electrolyte-cathode blank.
2.3 Using ethanol solution to clean the redundant slurry on the surface of the embryo body, and obtaining the composite 3D structure anode-solid electrolyte-cathode.
3) And respectively assembling aluminum foil and copper foil on the positive electrode side and the negative electrode side of the composite 3D structure positive electrode-solid electrolyte-negative electrode, enhancing the binding force of each part of the battery through rolling treatment, and then packaging the battery to obtain the PEO-based polymer solid-state battery with the composite 3D structure.
Example 2 preparation of PAN-based Polymer solid State batteries
In this embodiment, the PAN-based polymer solid-state battery of the composite 3D structure is composed of a positive electrode current collector, a composite 3D structure "positive electrode-solid electrolyte-negative electrode", and a negative electrode current collector. Wherein the thickness of the solid-state battery is 2.7mm, the thickness of the positive electrode current collector (aluminum foil) is 16 mu m, and the thickness of the negative electrode current collector (copper foil) is 10 mu m; the positive pole and the negative pole are of a three-period minimum curved surface structure Gyroid, the size of a structural unit is 0.25mm, and the relative density is 40%; meanwhile, the extension length of the positive electrode post along the direction vertical to the current collector is 2mm, and the extension length of the negative electrode post along the direction vertical to the current collector is 2.5mm; the positive and negative electrode spacing was 15 μm in the case of the cross arrangement.
In this example, the positive electrode active material was lithium cobaltate, the conductive agent was acetylene black, the binder was polyvinylidene fluoride (PVDF), and dispersion was performed using nitrogen-methylpyrrolidone (NMP); the negative electrode active material is artificial graphite, the binder is polyacrylic acid (PAA), and simultaneously acetone solution is selected for dispersion; the solid electrolyte material is Polyacrylonitrile (PAN) and LiClO 4 。
The preparation process of the PAN-based polymer solid-state battery provided by the example comprises the following steps:
1) Preparing positive printing slurry, negative printing slurry and solid electrolyte slurry;
1.1 Raw materials required for preparing the printable slurry, including a positive electrode active material, a conductive agent, a negative electrode active material, a solid electrolyte material, and a binder.
Pretreatment of solid electrolyte material: placing polyacrylonitrile in a vacuum drying oven with the temperature of 40 ℃ for drying treatment for 12 hours; at the same time LiClO 4 Drying in a vacuum drying oven at 100deg.C for 12 hr;
electrode material treatment: the lithium cobaltate and acetylene black materials in a certain proportion are weighed and mixed, and then ground for 18 hours in a ball mill at a speed of 350 r/min.
1.2 Using the material after pretreatment in step 1.1) to formulate a printable slurry: the components are mixed according to the required proportion and mechanically stirred, and finally the printing slurry with proper rheological property and stable property is obtained. The solid phase part of the positive printing slurry comprises 80% of lithium cobaltate, 12% of acetylene black and 8% of polyvinylidene fluoride (PVDF), wherein the mass ratio of nitrogen-methyl pyrrolidone (NMP) to the solid phase is 1:9, a step of performing the process; the solid phase part of the negative electrode printing slurry comprises 80% of artificial graphite and 20% of polyacrylic acid (PAA), and the mass ratio of the acetone solution to the solid phase is 1:9, a step of performing the process; polyacrylonitrile (PAN) and LiClO in solid electrolyte slurry 4 The molar ratio of (2) is 18:1.
2) Printing and forming of the anode-solid electrolyte-cathode by using multi-material 3D printing equipment, wherein the specific implementation forms are as follows:
2.1 Respectively placing the printable slurries prepared in the step 1) in different feeding devices, and establishing a corresponding relation between forming materials and the numbers of the feeding devices in a control system of the multi-material printing equipment; a cleaning device containing ethanol solution is arranged on one workbench of the multi-material 3D printing equipment and is used for cleaning parts in the forming process.
2.2 In the multi-material 3D printing forming process, the industrial control system extracts information of each material distribution area of each layer of the multi-material part according to the slicing file, and realizes the multi-material nested printing process by converting feeding devices filled with different printing pastes into a working area, so as to obtain a composite 3D structure anode-solid electrolyte-cathode blank.
2.3 Using ethanol solution to clean the redundant slurry on the surface of the embryo body, and obtaining the composite 3D structure anode-solid electrolyte-cathode.
3) And respectively assembling aluminum foil and copper foil on the positive electrode side and the negative electrode side of the composite 3D structure positive electrode-solid electrolyte-negative electrode, enhancing the binding force of each part of the battery through rolling treatment, and then packaging the battery to obtain the PAN-based polymer solid-state battery with the composite 3D structure.
The above are two preferred embodiments of the present invention, but the technical content of the protection of the present invention is not limited thereto. In embodiments, the selection and combination of the individual structural parameters, 3D printing process, and paste composition may be replaced with the corresponding ones disclosed in the application document to obtain a solid state battery.
Claims (10)
1. A solid-state battery characterized in that: the solid-state battery comprises a positive current collector (1), a negative current collector (3) and a composite 3D structure (2); the composite 3D structure (2) comprises a positive electrode (4), a negative electrode (5) and a solid electrolyte (6); the solid electrolyte (6) is arranged between the positive electrode current collector (1) and the negative electrode current collector (3); the positive electrode (4) is arranged on the positive electrode current collector (1) and extends into the solid electrolyte (6) along the direction from the positive electrode current collector (1) to the negative electrode current collector (3); the negative electrode (5) is arranged on the negative electrode current collector (3) and extends into the solid electrolyte (6) along the direction from the negative electrode current collector (3) to the positive electrode current collector (1).
2. The solid-state battery according to claim 1, wherein: the positive electrodes (4) and the negative electrodes (5) are all multiple, and the positive electrodes (4) and the negative electrodes (5) are arranged in a staggered and parallel mode.
3. The solid-state battery according to claim 2, wherein: among the positive electrode (4) and the negative electrode (5), the distance between the adjacent positive electrode (4) and negative electrode (5) is 10-20 [ mu ] m.
4. A solid state battery according to claim 3, characterized in that: the length of the positive electrode (4) extending from the positive electrode current collector (1) into the solid electrolyte (6) is 1.0-3.5 mm.
5. The solid-state battery according to claim 4, wherein: the length of the negative electrode (5) extending into the solid electrolyte (6) from the negative electrode current collector (3) is 1.5-4.0 mm.
6. The solid-state battery according to any one of claims 1 to 5, wherein: the positive electrode (4) and the negative electrode (5) are of three-period minimum curved surface structures.
7. The solid-state battery according to claim 6, wherein: the thicknesses of the positive electrode current collector (1) and the negative electrode current collector (3) are 10-20 mu m; the total thickness of the solid-state battery is 1.7 to 4.2mm.
8. A method for producing the solid-state battery according to claim 7, characterized in that: the method comprises the following steps:
1) Preparing raw materials; the raw materials comprise a positive electrode active material, a conductive agent, a negative electrode active material, a solid electrolyte material and a binder;
2) Configuring printable slurry according to the raw materials prepared in step 1); the printable slurry comprises positive electrode printing slurry, negative electrode printing slurry and solid electrolyte slurry;
3) Printing the printable slurry obtained in the step 2) based on a multi-material 3D printing mode to form a composite 3D structure (2);
4) Respectively assembling an anode current collector (1) and a cathode current collector (3) on the 3D structure (2) prepared in the step 3), and packaging the battery after rolling treatment to obtain a solid-state battery;
preferably, in the step 1), the positive electrode active material is one or more of lithium iron phosphate, lithium manganate, lithium cobaltate, lithium titanate and ternary materials; the conductive agent is superp, conductive carbon black and acetyleneOne or more of black, graphene, and carbon nanotubes; the negative electrode active material is one or more of graphite, carbon black, graphene, silicon-carbon alloy, metallic lithium and alloy thereof; the binder comprises polyvinylpyrrolidone (PVP) and polyvinylidene fluoride (PVDF); the solid electrolyte material is polymer electrolyte and lithium salt; the polymer electrolyte is polyethylene oxide (PEO) and Polyacrylonitrile (PAN), and the lithium salt is LiTFSI or LiClO 4 And LiBF 4 ；
In the step 2), the positive electrode printing slurry comprises a positive electrode active material, a conductive agent and a binder; the negative electrode printing slurry comprises a negative electrode active material and a binder; the solid electrolyte slurry includes an electrolyte material and a binder; the printable slurry is configured in the following way: the raw materials used for printing paste are mixed according to the required proportion, and the printing paste with proper rheological property and stable property is obtained after mechanical stirring and even stirring.
9. The method according to claim 7 or 8, characterized in that: the step 3) is specifically as follows:
3.1 Respectively placing the printable slurry prepared in the step 2) into different feeding devices of the multi-material 3D printing equipment;
3.2 Obtaining a blank composed of a positive electrode, a solid electrolyte and a negative electrode based on a multi-material 3D printing mode;
3.3 Cleaning the embryo body prepared in the step 3.2) to obtain a composite 3D structure (2) consisting of a positive electrode, a solid electrolyte and a negative electrode;
in the step 4), the positive current collector (1) is aluminum foil; the negative electrode current collector (3) is copper foil.
10. A solid-state battery prepared based on the method of claim 9.
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