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CN114865096B - Method for preparing solid-state lithium ion battery by 3D printing and lithium ion battery obtained by method - Google Patents

Method for preparing solid-state lithium ion battery by 3D printing and lithium ion battery obtained by method

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Publication number
CN114865096B
CN114865096B CN202210568486.3A CN202210568486A CN114865096B CN 114865096 B CN114865096 B CN 114865096B CN 202210568486 A CN202210568486 A CN 202210568486A CN 114865096 B CN114865096 B CN 114865096B
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lithium
printing
ink
positive electrode
photo
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CN114865096A (en
Inventor
王萌
苏岳锋
李宁
陈来
黄擎
卢赟
曹端云
吴锋
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Chongqing Innovation Center of Beijing University of Technology
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Chongqing Innovation Center of Beijing University of Technology
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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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

本发明公开了一种利用3D打印制备固态锂离子电池的方法及得到的锂离子电池，包括以下步骤：S1、制备正极墨水、负极墨水和复合电解质墨水；S2、将正极墨水置于3D打印机针筒中，在玻璃基板上逐层打印并同时进行光固化，得到3D打印正极；S3、将复合电解质墨水置于3D打印机针筒中，在正极表面逐层打印并同时进行光固化，得到电解质；S4、将负极墨水置于3D打印机针筒中，在电解质表面逐层打印并同时进行光固化；S5、外层打印封装即得。本发明的方法结合了墨水直写成型和光固化成型的优点，可以实现3D打印一体化连续制备固态电池，提高了固态电解质与电极间紧密结合度，无需传统光固化工艺脱脂且无需大量添加剂，简化了配方和成型流程，整个打印制备过程避免了传统电池制备过程中所需的集流体、粘结剂、干燥、极片压实、组装、热塑封等过程，极大简化了制备工艺。

The present invention discloses a method for preparing a solid-state lithium-ion battery using 3D printing and the obtained lithium-ion battery, comprising the following steps: S1, preparing positive electrode ink, negative electrode ink and composite electrolyte ink; S2, placing the positive electrode ink in a 3D printer syringe, printing layer by layer on a glass substrate and simultaneously performing photocuring to obtain a 3D printed positive electrode; S3, placing the composite electrolyte ink in a 3D printer syringe, printing layer by layer on the surface of the positive electrode and simultaneously performing photocuring to obtain an electrolyte; S4, placing the negative electrode ink in a 3D printer syringe, printing layer by layer on the surface of the electrolyte and simultaneously performing photocuring; S5, printing and packaging the outer layer. The method of the present invention combines the advantages of ink direct writing molding and photocuring molding, can realize 3D printing integrated continuous preparation of solid-state batteries, improves the close bonding between the solid electrolyte and the electrode, does not require degreasing in the traditional photocuring process and does not require a large amount of additives, simplifies the formula and molding process, and the entire printing preparation process avoids the processes of current collector, binder, drying, pole piece compaction, assembly, thermal plastic sealing, etc. required in the traditional battery preparation process, greatly simplifying the preparation process.

Description

Method for preparing solid-state lithium ion battery by 3D printing and lithium ion battery obtained by method
Technical Field
The invention relates to the technical field of lithium ion battery preparation, in particular to a method for preparing a solid lithium ion battery by utilizing 3D printing and the obtained lithium ion battery.
Background
With the rapid development of new energy automobiles and the increase of the demand of new energy storage of power grid development, the energy density and the safety performance of batteries are more and more urgent. Most of traditional lithium ion batteries adopt liquid organic electrolyte, which is inflammable and decomposed under high pressure, so that the safety performance of the battery is poor. The appearance of solid-state batteries can effectively solve the defects, can obviously improve the energy density and the safety performance of the batteries, and is a necessary trend of future development of lithium ion batteries. One of the technical difficulties of solid-state batteries is to improve the stability of the solid interface between the electrolyte and the electrode and promote the ion migration rate. However, the traditional solid-state battery preparation method is that electrodes and electrolytes are prepared respectively and then assembled, and the method is not beneficial to improving the tightness of a solid-solid interface, so that the interface impedance is increased, and the process flow is long in time consumption.
The 3D printing technology which is rising in recent years can thoroughly change the traditional planar electrode structure, and can customize the electrode and solid electrolyte structure with complex three-dimensional structures according to requirements, thereby being beneficial to shortening the lithium ion migration distance and improving the lithium ion diffusion rate. However, the current 3D printing technology for preparing the lithium ion battery is complex in process, the positive electrode and the negative electrode are usually printed out separately, and then the battery is assembled with the electrolyte in a glove box, so that the process is complicated and time-consuming, and the advantage of 3D printing cannot be fully utilized. Meanwhile, various non-electrochemical active forming agents are required to be added in the printing process, so that the electrochemical performance of the battery is not facilitated. For example, the use of highly sensitive photo-curing techniques requires the addition of relatively large amounts of photosensitive resin materials, but such materials are inherently non-conductive and require degreasing and demolding processes, and existing photo-curing printing techniques have substantial limitations in terms of electrode and electrolyte preparation. For the ink direct writing technology with wide applicable materials, the ink has higher rheological property requirement, various large amounts of forming agents are required to be added to meet the printing requirement, the added additives have larger negative influence on the electrode performance, the printing ink often contains more water or other solvents, the final electrode can be obtained by subsequent freeze drying or heat treatment, and the process is more complicated.
Disclosure of Invention
The invention aims to provide a method for preparing a solid lithium ion battery by utilizing 3D printing and the obtained lithium ion battery, aiming at the problems, and the invention provides a 3D printing technology which is simple in flow and capable of integrally and continuously preparing the solid lithium ion battery, so that the defects of the conventional 3D printing lithium ion battery are overcome, a large amount of additives in degreasing and direct writing processes in the traditional photocuring process are not needed, the forming ink formula and the printing process are simplified, and the obtained solid lithium ion battery is high in bonding degree of an electrode and an electrolyte interface, the solid interface impedance is reduced, the lithium ion migration capability is improved, and the battery performance is obviously improved. The technical scheme adopted by the invention is as follows, the method for preparing the solid-state lithium ion battery by utilizing 3D printing comprises the following steps:
s1, taking positive electrode, negative electrode and composite electrolyte ink, respectively and uniformly stirring on a magnetic stirrer to obtain positive electrode ink, negative electrode ink and composite electrolyte ink respectively;
S2, placing the positive electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate, and performing photo-curing simultaneously to obtain a 3D printing positive electrode;
s3, placing the composite electrolyte ink in a needle cylinder of a 3D printer, setting printer parameters, printing layer by layer on the surface of the positive electrode printed in the S2, and simultaneously performing photo-curing to obtain an electrolyte tightly combined with the surface of the positive electrode;
s4, placing the negative electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on the surface of the electrolyte printed in the S3, and performing photo-curing simultaneously to obtain a negative electrode tightly combined with the surface of the electrolyte, thereby obtaining a positive electrode/electrolyte/negative electrode battery structural member;
s5, stripping the battery structural member obtained in the S4 from the glass plate, and printing and packaging the outer layer, wherein the packaging material is photosensitive epoxy resin.
According to the invention, on one hand, the tight combination degree between the solid electrolyte and the electrode can be improved, the integrated forming technology is beneficial to improving the compatibility of the electrode/electrolyte interface and promoting the migration of lithium ions, and on the other hand, the advantages of the ink direct writing forming technology and the photo-curing forming technology are combined, the ink formula is improved without the subsequent sintering degreasing process of the traditional photo-curing technology and without a large amount of non-electrochemical active additives in the direct writing technology, so that the forming ink formula and the printing flow are simplified, the application obstruction of the 3D printing technology in the solid lithium ion battery is overcome, and the process scale is facilitated. In addition, the whole process avoids the processes of current collector, binder, drying, pole piece compaction, assembly, thermoplastic sealing and the like required in the traditional battery preparation process, realizes full-process 3D printing, greatly simplifies the preparation process, and has the advantages of high energy density, good cycle performance and the like.
In the invention, the positive electrode, the negative electrode and the composite electrolyte are cured and formed in a light curing mode, so that the use of a binder in the electrode is avoided, sintering degreasing, compaction and other processes are not needed in the follow-up process, and in order to achieve the purpose, the positive electrode ink, the negative electrode ink and the composite electrolyte ink all contain light curing functional agents (the light curing functional agents have little addition and have no negative effect on lithium ion migration due to the fact that the selected polymer monomers have no obvious and negligible effect on the electrochemical properties of the positive electrode, the negative electrode and the composite electrolyte), the light curing functional agents comprise the polymer monomers and the photoinitiator, and the mass ratio of the polymer monomers to the photoinitiator is 50-150:1, for example, 50:1, 55:1, 70:1, 80:1, 90:1, 100:1, 110:1, 115:1, 120:1, 125:1, 130:1, 150:1 and the like.
Further, the polymer monomer is selected from one or more of hydroxyethyl acrylate, trimethylolpropane triacrylate, polyethylene glycol methacrylate, polyethylene glycol diacrylate, methoxy polyethylene glycol methacrylate, epoxycyclohexane, ethoxylated trimethylpropane triacrylate, methacrylate and hexanediol diacrylate, and the photoinitiator is one or more of trimethylbenzoyl-diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-dimethylolpropionic acid and xylene ketone.
Further, the positive electrode ink comprises, by mass, 1% -10% of a photo-curing functional agent, 75% -90% of a positive electrode active material, 2% -10% of a conductive agent and 1% -8% of a dispersing agent (the dispersing agent selected below is extremely volatile, the addition amount is small, the volatilization is assisted by a heating pad arranged later, and processes such as drying are not required). In the positive electrode ink of the present invention, the doping amount of the photo-curing functional agent may be specifically 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., the doping amount of the positive electrode active material may be specifically 75%, 80%, 85%, 90%, etc., the doping amount of the conductive agent may be specifically 2%, 3%, 4%, 5%, 5.5%, 6%, 7%, 8%, 10%, etc., and the doping amount of the dispersant may be adaptively adjusted according to actual needs, without special requirements.
Further, the positive electrode active material is selected from one or more of lithium cobaltate, lithium iron phosphate, lithium manganate, nickel cobalt manganese ternary, nickel cobalt aluminum material and manganese-based lithium-rich material, the conductive agent is selected from one or more of conductive carbon black, conductive graphite, carbon nano tube, acetylene black, graphene and carbon fiber, and the dispersing agent is selected from one or more of polyacrylic acid, acetonitrile, N-methylpyrrolidone, dimethylacetamide, ethanol, glycerol, ethylene carbonate and propylene carbonate. Further, the light-curing functional agent is not suitable to be mixed in too much or too little, if the mixing amount is too much, the electrochemical performance of the material is not exerted, and if the mixing amount is too little, the electrode cannot be completely cured and molded.
In the invention, the negative electrode ink comprises, by mass, 1% -10% of a photo-curing functional agent, 75% -90% of a negative electrode active material, 2% -10% of a conductive agent and 1% -8% of a dispersing agent (the solvent selected below is extremely volatile, the addition amount is small, and the volatilization is assisted by a heating pad arranged later, and a drying process and the like are not required). In the negative electrode ink, the doping amount of the photo-curing functional agent can be specifically 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and the like, the doping amount of the negative electrode active material can be specifically 75%, 80%, 85%, 90% and the like, the doping amount of the conductive agent can be specifically 2%, 3%, 4%, 5%, 5.5%, 6%, 7%, 8%, 10% and the like, and the doping amount of the dispersing agent is adaptively adjusted according to actual needs without special requirements.
Further, the anode active material is selected from one or more of graphite, silicon carbon and lithium titanate, the conductive agent is selected from one or more of conductive carbon black, conductive graphite, carbon nano tube, acetylene black, graphene and carbon fiber, and the dispersing agent is selected from one or more of polyacrylic acid, acetonitrile, N-methylpyrrolidone, dimethylacetamide, ethanol, glycerol, ethylene carbonate and propylene carbonate. Accordingly, the light-curing functional agent is not suitable to be mixed too much or too little, if the mixing amount is too much, the electrochemical performance of the material is not exerted, and if the mixing amount is too little, the electrode cannot be completely cured and molded.
In the invention, the composite electrolyte ink comprises, by mass, 1% -10% of a photo-curing functional agent, 45% -75% of a polymer, 1% -20% of a lithium salt, 1% -20% of ion conductive powder and 1% -10% of an organic solvent. In the composite electrolyte ink, the specific doping amount of the photo-curing functional agent can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and the like, the specific doping amount of the polymer can be 45%, 50%, 55%, 60%, 65%, 70%, 75% and the like, the specific doping amount of the lithium salt can be 1%, 6%, 8%, 9%, 10%, 12%, 15%, 17%, 18%, 20% and the like, the specific doping amount of the ion conductive powder can be 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20% and the like, and the doping amount of the organic solvent is adaptively adjusted according to actual needs without special requirements.
Further, the polymer is selected from one or more of polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, polyvinylidene fluoride, polyvinyl chloride, polyvinyl alcohol, polyacrylic acid, polyethyl acetate, polyethylene glycol divinyl ether and polycaprolactone, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium difluorosulfimide, lithium tetrafluoroborate, lithium perchlorate, lithium bisoxalato borate, lithium hexafluoroarsenate, lithium bisoxalato borate, lithium trifluoromethane sulfonate and lithium bistrifluoromethylsulfonimide, the ion conductive powder is selected from one or more of Lithium Lanthanum Zirconium Oxide (LLZO), lithium Lanthanum Titanium Oxide (LLTO), titanium aluminum lithium phosphate (LATP) and germanium aluminum lithium phosphate (LAGP), and the organic solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, methyl formate, dimethoxy methane, ethylene carbonate and propylene carbonate. Further, in the composite electrolyte ink, the doping amount of the photo-curing functional agent is not suitable to be too large or too small, the lithium ion migration is unfavorable when the doping amount is too large, and the electrolyte cannot be completely cured and molded when the doping amount is too small.
Further, in the case of photo-curing, the light source used for photo-curing is in the wavelength range of 100nm to 500nm and the intensity is 1000mW/cm 2-4000 mW/cm2.
Further, in order to avoid the processes such as drying the positive electrode after printing, in S2, a heating pad is placed under the glass substrate, and the glass substrate is heated by the heating pad, so that the positive electrode on the glass substrate is dried, and the heating temperature of the heating pad is 35-200 ℃. The invention not only does not influence the printing process and the printing quality of the anode by the mode of simultaneous printing and heating drying, but also saves the time consumption of the process, shortens the process flow and is beneficial to realizing industrialization.
The invention further provides a solid-state lithium ion battery, which is prepared by the method.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. The method can realize the continuous preparation of the solid-state battery by 3D printing, improves the tight combination degree between the solid-state electrolyte and the electrodes, is favorable for improving the compatibility of a solid interface and promoting the migration of lithium ions, improves the traditional 3D printing process by combining the advantages of the direct writing forming and photo-curing forming technology of ink, does not need the subsequent sintering degreasing process of the traditional photo-curing process and does not need a large amount of non-electrochemical active additives in the direct writing process, simplifies the forming ink formula and the printing process, overcomes the application obstruction of the 3D printing technology in the solid-state lithium ion battery, is favorable for process scale, and avoids the processes of current collector, drying, pole piece compaction, assembly, thermoplastic sealing and the like required in the traditional battery preparation process by the whole printing preparation process;
2. The invention adopts 3D printing technology to accurately regulate the morphology and structure of the electrolyte and the electrode, is beneficial to large-scale manufacture, can improve the ion transmission rate between the electrode and the solid electrolyte, has simple preparation process, no calcining or heat treatment step, avoids time and energy consumption, simultaneously adopts a small amount of photocuring agent to replace binder, avoids the use of more binders (such as polyvinylidene fluoride, carboxymethyl cellulose and the like) in the traditional electrode, improves the content of active substances in the electrode sheet, seamlessly integrates the battery, and omits the processes of extra solvent drying and the like.
Drawings
Fig. 1 is a schematic structural diagram of a solid-state lithium ion battery prepared by 3D printing according to the present invention;
FIG. 2 is a graph of the cycle at 1.0C for the cell of example 1;
fig. 3 is a first charge-discharge curve at 0.1C for the battery of example 2.
In fig. 1, 1 is a tab, 2 is a solid electrolyte, 3 is a positive electrode, and 4 is a negative electrode.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 1, a method for preparing a solid-state lithium ion battery using 3D printing includes the steps of:
S1, taking anode, cathode and composite electrolyte ink, respectively stirring uniformly on a magnetic stirrer to obtain anode ink, cathode ink and composite electrolyte ink, wherein the anode ink comprises 1% -10% of photo-curing functional agent, 75% -90% of anode active material, 2% -10% of conductive agent and 1% -8% of dispersing agent, the anode active material is selected from one or more of lithium cobaltate, lithium iron phosphate, lithium manganate, nickel cobalt manganese ternary, nickel cobalt aluminum material and manganese-based lithium-rich material, the conductive agent is selected from one or more of conductive carbon black, conductive graphite, carbon nano tube, acetylene black, graphene and carbon fiber, and the dispersing agent is selected from polyacrylic acid, Acetonitrile, N-methyl pyrrolidone, dimethylacetamide, ethanol, glycerol, ethylene carbonate and propylene carbonate, wherein the negative electrode ink comprises 1-10% of photo-curing functional agent, 75-90% of negative electrode active material, 2-10% of conductive agent and 1-8% of dispersing agent, the negative electrode active material is selected from one or more of graphite, silicon carbon and lithium titanate, the conductive agent is selected from one or more of conductive carbon black, conductive graphite, carbon nano tube, acetylene black, graphene and carbon fiber, and the dispersing agent is selected from polyacrylic acid, acetonitrile, N-methyl pyrrolidone, dimethylacetamide, ethanol, The composite electrolyte ink comprises 1% -10% of photo-curing functional agent, 45% -75% of polymer, 1% -20% of lithium salt, 1% -20% of ion conductive powder and 1% -10% of organic solvent, wherein the polymer is selected from one or more of polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, polyvinylidene fluoride, polyvinyl chloride, polyvinyl alcohol, polyacrylic acid, polyethyl acetate, polyethylene glycol divinyl ether and polycaprolactone, and the lithium salt is selected from lithium hexafluorophosphate, lithium difluorosulfonimide, lithium tetrafluoroborate, The lithium ion conductive powder is selected from one or more of lithium perchlorate, lithium bisoxalato borate, lithium hexafluoroarsenate, lithium bisoxalato borate, lithium trifluoromethane sulfonate and lithium bistrifluoromethylsulfonyl imide, the ion conductive powder is selected from one or more of Lithium Lanthanum Zirconium Oxide (LLZO), lithium Lanthanum Titanium Oxide (LLTO), titanium aluminum phosphate lithium compound (LATP) and germanium aluminum lithium phosphate compound (LAGP), the organic solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, methyl formate, dimethoxymethane, ethylene carbonate and propylene carbonate, the photocuring functional agent comprises a polymer monomer and a photoinitiator, the mass ratio of the polymer monomer to the photoinitiator is 50-150:1, and the polymer monomer is selected from hydroxyethyl acrylate, One or more of trimethylol propane triacrylate, polyethylene glycol methacrylate, polyethylene glycol diacrylate, methoxy polyethylene glycol methacrylate, epoxycyclohexane, ethoxylated trimethylpropane triacrylate, methacrylate and hexanediol diacrylate, wherein the photoinitiator is one or more of trimethylbenzoyl-diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-dimethylol propionic acid and xylene ketone;
S2, placing the positive electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate, and performing photo-curing simultaneously to obtain a 3D printing positive electrode;
s3, placing the composite electrolyte ink in a needle cylinder of a 3D printer, setting printer parameters, printing layer by layer on the surface of the positive electrode printed in the S2, and simultaneously performing photo-curing to obtain an electrolyte tightly combined with the surface of the positive electrode;
s4, placing the negative electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on the surface of the electrolyte printed in the S3, and performing photo-curing simultaneously to obtain a negative electrode tightly combined with the surface of the electrolyte, thereby obtaining a positive electrode/electrolyte/negative electrode battery structural member;
s5, stripping the battery structural member obtained in the S4 from the glass plate, and printing and packaging the outer layer, wherein the packaging material is photosensitive epoxy resin.
For a better illustration of the invention, specific examples are set forth below:
Example 1
A method for preparing a high-nickel ternary NCM811 type solid-state lithium ion battery by 3D printing comprises the following steps:
S1, taking an anode, a cathode and composite electrolyte ink, respectively stirring uniformly on a magnetic stirrer to obtain the anode ink, the cathode ink and the composite electrolyte ink, wherein the anode ink comprises 5% of a photo-curing functional agent, 85% of a high-nickel ternary NCM811 material, 5% of conductive carbon black and 5% of N-methyl pyrrolidone, the cathode ink comprises 7% of the photo-curing functional agent, 85% of a graphite material, 5% of acetylene black and 3% of N-methyl pyrrolidone, the composite electrolyte ink comprises 2% of the photo-curing functional agent, 75% of polyvinylidene fluoride-hexafluoropropylene copolymer, 5% of lithium hexafluorophosphate, 15% of lithium lanthanum zirconium oxide compound and 3% of dimethyl carbonate, and the photo-curing functional agent comprises polymer monomer polyethylene glycol diacrylate and photoinitiator trimethyl benzoyl-diphenyl phosphine oxide, wherein the mass ratio of the polymer monomer to the photoinitiator is 100:1;
S2, placing the positive electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate at a printing speed of 20mL/min at a temperature of 100 ℃ and simultaneously performing photo-curing, wherein the wavelength of a light source is 405nm, and the intensity is 4000mW/cm 2, so as to obtain a 3D printing positive electrode;
S3, placing the composite electrolyte ink in a cylinder of a 3D printer, setting printer parameters, printing the positive electrode surface printed in the S2 layer by layer at a printing speed of 20mL/min, and simultaneously performing photo-curing, wherein the light source wavelength is 405nm, and the intensity is 4000mW/cm 2, so as to obtain the electrolyte tightly combined with the positive electrode surface;
S4, placing the negative electrode ink into a cylinder of a 3D printer, setting printer parameters, printing the surface of the electrolyte printed in the S3 layer by layer at a printing speed of 20mL/min, and simultaneously performing photo-curing, wherein the wavelength of a light source is 405nm, and the intensity is 4000mW/cm 2, so as to obtain a negative electrode tightly combined with the surface of the electrolyte, and further obtain a positive electrode/electrolyte/negative electrode battery structural member;
S5, stripping the battery structural member obtained in the S4 from the glass plate, printing and packaging the outer layer at a printing speed of 30mL/min, wherein the packaging material is photosensitive epoxy resin, the light source wavelength is 405nm, and the intensity is 4000mW/cm 2.
Example 2
A method for preparing a high-nickel ternary NCM622 type solid-state lithium ion battery by 3D printing comprises the following steps:
S1, taking an anode, a cathode and composite electrolyte ink, respectively stirring uniformly on a magnetic stirrer to obtain the anode ink, the cathode ink and the composite electrolyte ink, wherein the anode ink comprises 1% of a photo-curing functional agent, 90% of a high-nickel ternary NCM622 material, 4% of conductive carbon black and 5% of N-methyl pyrrolidone, the cathode ink comprises 1% of the photo-curing functional agent, 90% of a silicon carbon material, 6% of acetylene black and 3% of N-methyl pyrrolidone, the composite electrolyte ink comprises 2% of the photo-curing functional agent, 75% of polyacrylic acid, 5% of lithium difluorosulfimide, 15% of lithium lanthanum titanium oxide and 3% of ethylene carbonate, and the photo-curing functional agent comprises polymer monomer ethoxylated trimethylolpropane triacrylate and photo-initiator 2-hydroxy-2-methyl 1-phenyl 1-acetone, wherein the mass ratio of the polymer monomer to the photo-initiator is 80:1;
S2, placing the positive electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate at 120 ℃ at a printing speed of 10mL/min, and simultaneously performing photo-curing, wherein the wavelength of a light source is 365nm, and the intensity is 4000mW/cm 2, so as to obtain a 3D printing positive electrode;
S3, placing the composite electrolyte ink in a cylinder of a 3D printer, setting printer parameters, printing the positive electrode surface printed in the S2 layer by layer at a printing speed of 10mL/min, and simultaneously performing photo-curing, wherein the light source wavelength is 365nm, and the intensity is 4000mW/cm 2, so as to obtain the electrolyte tightly combined with the positive electrode surface;
S4, placing the negative electrode ink into a cylinder of a 3D printer, setting printer parameters, printing the surface of the electrolyte printed in the S3 layer by layer at a printing speed of 10mL/min, and simultaneously performing photo-curing, wherein the wavelength of a light source is 365nm, and the intensity is 4000mW/cm 2, so as to obtain a negative electrode tightly combined with the surface of the electrolyte, and further obtain a positive electrode/electrolyte/negative electrode battery structural member;
S5, stripping the battery structural member obtained in the S4 from the glass plate, printing and packaging the outer layer at a printing speed of 30mL/min, wherein the packaging material is photosensitive epoxy resin, the light source wavelength is 365nm, and the intensity is 4000mW/cm 2.
Example 3
A method for preparing a Li 1.2Mn0.54Ni0.13Co0.13O2 solid-state lithium ion battery by 3D printing, comprising the steps of:
s1, taking an anode, a cathode and composite electrolyte ink, respectively stirring uniformly on a magnetic stirrer to obtain the anode ink, the cathode ink and the composite electrolyte ink, wherein the anode ink comprises 4% of a photo-curing functional agent, 80% of a Li 1.2Mn0.54Ni0.13Co0.13O2 material, 8% of conductive carbon black and 8% of ethanol, the cathode ink comprises 1% of the photo-curing functional agent, 80% of a lithium titanate material, 10% of acetylene black and 9% of ethanol, the composite electrolyte ink comprises 2% of the photo-curing functional agent, 76% of polyethylene oxide, 10% of lithium bisoxalato borate, 10% of a lithium lanthanum titanium oxide compound and 2% of ethylene carbonate, the photo-curing functional agent comprises polymer monomer ethoxylated trimethylolpropane triacrylate and a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, and the mass ratio of the polymer monomer to the photoinitiator is 50:1;
S2, placing the positive electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate at 90 ℃ at a printing speed of 5mL/min, and simultaneously performing photo-curing, wherein the wavelength of a light source is 365nm, and the intensity is 4000mW/cm 2, so as to obtain a 3D printing positive electrode;
S3, placing the composite electrolyte ink in a cylinder of a 3D printer, setting printer parameters, printing the positive electrode surface printed in the S2 layer by layer at a printing speed of 5mL/min, and simultaneously performing photo-curing, wherein the light source wavelength is 365nm, and the intensity is 4000mW/cm 2, so as to obtain the electrolyte tightly combined with the positive electrode surface;
S4, placing the negative electrode ink into a cylinder of a 3D printer, setting printer parameters, printing the surface of the electrolyte printed in the S3 layer by layer at a printing speed of 5mL/min, and simultaneously performing photo-curing, wherein the wavelength of a light source is 365nm, and the intensity is 4000mW/cm 2, so as to obtain a negative electrode tightly combined with the surface of the electrolyte, and further obtain a positive electrode/electrolyte/negative electrode battery structural member;
s5, stripping the battery structural member obtained in the S4 from the glass plate, printing and packaging the outer layer at a printing speed of 20mL/min, wherein the packaging material is photosensitive epoxy resin, the light source wavelength is 365nm, and the intensity is 4000mW/cm 2.
Comparative example 1
Taking the example 1 to prepare a high-nickel ternary NCM811 type solid-state lithium ion battery, adopting the existing 3D printing method to print out a positive electrode and a negative electrode separately, and then assembling the positive electrode and the negative electrode into the lithium ion battery, the steps are as follows:
S1, taking an anode, a cathode and composite electrolyte ink, respectively stirring uniformly on a magnetic stirrer to obtain the anode ink, the cathode ink and the composite electrolyte ink, wherein the anode ink comprises 5% of a photo-curing functional agent, 85% of a high-nickel ternary NCM811 material, 5% of conductive carbon black and 5% of N-methyl pyrrolidone, the cathode ink comprises 7% of the photo-curing functional agent, 85% of a graphite material, 5% of acetylene black and 3% of N-methyl pyrrolidone, the composite electrolyte ink comprises 2% of the photo-curing functional agent, 75% of polyvinylidene fluoride-hexafluoropropylene copolymer, 5% of lithium hexafluorophosphate, 15% of lithium lanthanum zirconium oxide compound and 3% of dimethyl carbonate, and the photo-curing functional agent comprises polymer monomer polyethylene glycol diacrylate and photoinitiator trimethyl benzoyl-diphenyl phosphine oxide, wherein the mass ratio of the polymer monomer to the photoinitiator is 100:1;
S2, placing the positive electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate at a printing speed of 20mL/min at a temperature of 100 ℃ and simultaneously performing photo-curing, wherein the wavelength of a light source is 405nm, and the intensity is 4000mW/cm 2, so as to obtain a 3D printing positive electrode;
s3, placing the composite electrolyte ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate at a printing speed of 20mL/min at a temperature of 100 ℃ and simultaneously performing photo-curing, wherein the wavelength of a light source is 405nm, and the intensity is 4000mW/cm 2, so as to obtain the 3D printing electrolyte;
s4, placing the negative electrode ink into a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate at a printing speed of 20mL/min at a temperature of 100 ℃ and performing simultaneous photo-curing, wherein the wavelength of a light source is 405nm, and the intensity is 4000mW/cm 2, so as to obtain a 3D printing negative electrode;
And S5, respectively placing the positive electrode and the negative electrode obtained in the steps S2 and S4 on two sides of the electrolyte printed in the step S3 to form a battery structural member, printing and packaging the battery structural member at the outer layer of the battery structural member at a printing speed of 30mL/min, wherein the packaging material is photosensitive epoxy resin, the wavelength of a light source is 405nm, and the intensity is 4000mW/cm 2.
Comparative example 2
Comparative example 2 was the same as example 1 except that the doping amount of the positive electrode photo-curing functional agent was 25%.
Comparative example 3
Comparative example 3 is the same as example 1 except that the amount of the photo-curing functional agent incorporated in the composite electrolyte was 35%.
Comparative example 4
Comparative example 4 is the same as example 1 except that the photo-curing functional agent contains a polymeric epoxy resin and a photoinitiator IRGACURE 819.
Comparative example 5
The positive electrode active material, the negative electrode active material, and the electrolyte used in comparative example 5 were the same as those in example 1, but the printing process was different.
A method for preparing a high-nickel ternary NCM811 solid-state lithium ion battery by printing through an ink direct writing forming technology comprises the following steps:
S1, taking an anode, a cathode and composite electrolyte ink, and uniformly stirring on a magnetic stirrer to obtain the anode ink, the cathode ink and the composite electrolyte ink respectively, wherein the anode ink comprises 10% of PVDF (polyvinylidene fluoride) -hexafluoropropylene copolymer, 5% of lithium hexafluorophosphate, 15% of lithium lanthanum zirconium oxide and 5% of dimethyl carbonate, and the cathode ink comprises 10% of PVDF (polyvinylidene fluoride) -hexafluoropropylene copolymer, 75% of high-nickel ternary NCM811 material, 10% of graphene and 5% of N-methyl pyrrolidone;
s2, placing the positive electrode ink in a cylinder of a 3D printer, setting printer parameters, and printing layer by layer on a glass substrate at 100 ℃ at a printing speed of 20 mL/min;
s3, placing the composite electrolyte ink in a needle cylinder of a 3D printer, setting printer parameters, and printing the surface of the positive electrode printed in the S2 layer by layer at a printing speed of 20mL/min to obtain an electrolyte tightly combined with the surface of the positive electrode;
S4, placing the negative electrode ink into a cylinder of a 3D printer, setting printer parameters, and printing the electrolyte surface printed in the S3 layer by layer at a printing speed of 20mL/min to obtain a negative electrode tightly combined with the electrolyte surface, thereby obtaining a positive electrode/electrolyte/negative electrode battery structural member;
and S5, stripping the battery structural member obtained in the S4 from the glass plate, and performing plastic package in a glove box by using aluminum foil.
Test analysis
The testing method comprises the following steps:
and carrying out charge and discharge test on the battery obtained by printing on a Land charge and discharge test instrument, wherein the test cut-off voltage is 2.8V-4.5V (1C=200 mAh/g).
Test results
Example 1, which has a discharge capacity of 188.7mAh/g at 0.1C rate and a coulombic efficiency of 88.8%, has a capacity retention rate of 95.7% after 50 weeks of cycling at 1.0C rate, as shown in FIG. 2, and has a discharge capacity of 162.6mAh/g at 5.0C. The battery prepared by 3D printing has higher discharge capacity, excellent cycle stability and good rate capability.
Example 2, which has a discharge capacity of 178.7mAh/g at 0.1C rate and a coulombic efficiency of 85.6%, has a capacity retention rate of 96.3% after 50 weeks of cycling at 1.0C rate, and has a discharge capacity of 159.2mAh/g at 5.0C, is shown in FIG. 3. The battery prepared by 3D printing has higher discharge capacity, excellent cycle stability and good rate capability.
Example 3, which has a discharge capacity of 258.6mAh/g at 0.1C rate and a coulombic efficiency of 80.3%, has a capacity retention rate of 88.7% after 50 weeks of cycling at 1.0C rate, and has a discharge capacity of 182.2mAh/g at 5.0C. The battery prepared by 3D printing has higher discharge capacity, excellent cycle stability and good rate capability.
Comparative example 1, which had a discharge capacity of 175.9mAh/g at a 0.1C rate and a coulombic efficiency of 83.1%, had a capacity retention rate of 87.7% after 50 weeks of cycle at a 1.0C rate and a discharge capacity of 140.6mAh/g at 5.0C. The performance of the battery obtained by respectively preparing the anode and the cathode and reassembling the electrolyte through 3D printing is inferior to that of the battery prepared continuously through 3D printing.
Comparative example 2, which has a discharge capacity of 170.1mAh/g at 0.1C rate and a coulombic efficiency of 80.8%, has a capacity retention rate of 80.9% after 50 weeks of cycling at 1.0C rate, and has a discharge capacity of 152.9mAh/g at 5.0C. It can be seen that excessive addition of the photo-curing functional agent in the positive electrode is unfavorable for the exertion of the electrochemical performance of the battery.
Comparative example 3, which has a discharge capacity of 180.1mAh/g at 0.1C rate and a coulombic efficiency of 87.8%, has a capacity retention rate of 89.3% after 50 weeks of cycling at 1.0C rate, and has a discharge capacity of only 141.3mAh/g at 5.0C. It can be seen that excessive addition of the photo-curing functional agent in the composite electrolyte is unfavorable for the exertion of the electrochemical performance of the battery.
Comparative example 4 has a discharge capacity of only 141.5mAh/g at 0.1C rate, a coulombic efficiency of 75.6%, a capacity retention rate of only 65.2% after 50 weeks of cycling at 1.0C rate, and a discharge capacity of only 91.3mAh/g at 5.0C. The selection of the visible light curing functional agent is very important to the quality of the electrochemical performance of the battery.
Comparative example 5 has a discharge capacity of only 135.1mAh/g at 0.1C rate, a coulombic efficiency of 72.2%, a capacity retention of only 56.7% after 50 weeks of cycling at 1.0C rate, and a discharge capacity of only 68.9mAh/g at 5.0C. In the ink direct writing printing process, relatively more binder is required to be added to promote the forming of a printing piece, so that the quantity of active matters in an electrode is relatively small, and the technology is not suitable for electrolyte printing due to excessive additives and prevents lithium ion migration. The ink direct-writing printing technique is not suitable for solid-state battery integrated continuous printing.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (7)

1. A method for preparing a solid-state lithium ion battery by 3D printing, comprising the steps of:
s1, taking positive electrode, negative electrode and composite electrolyte ink, respectively and uniformly stirring on a magnetic stirrer to obtain positive electrode ink, negative electrode ink and composite electrolyte ink respectively;
S2, placing the positive electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on a glass substrate, and performing photo-curing simultaneously to obtain a 3D printing positive electrode;
s3, placing the composite electrolyte ink in a needle cylinder of a 3D printer, setting printer parameters, printing layer by layer on the surface of the positive electrode printed in the S2, and simultaneously performing photo-curing to obtain an electrolyte tightly combined with the surface of the positive electrode;
s4, placing the negative electrode ink in a cylinder of a 3D printer, setting printer parameters, printing layer by layer on the surface of the electrolyte printed in the S3, and performing photo-curing simultaneously to obtain a negative electrode tightly combined with the surface of the electrolyte, thereby obtaining a positive electrode/electrolyte/negative electrode battery structural member;
S5, stripping the battery structural member obtained in the S4 from the glass plate, and printing and packaging the outer layer, wherein the packaging material is photosensitive epoxy resin;
The positive electrode ink comprises, by mass, 1% -10% of a photo-curing functional agent, 75% -90% of a positive electrode active material, 2% -10% of a conductive agent and 1% -8% of a dispersing agent;
the negative electrode ink comprises, by mass, 1% -10% of a photo-curing functional agent, 75% -90% of a negative electrode active material, 2% -10% of a conductive agent and 1% -8% of a dispersing agent;
The composite electrolyte ink comprises, by mass, 1% -10% of a photo-curing functional agent, 45% -75% of a polymer, 1% -20% of lithium salt, 1% -20% of ion conductive powder and 1% -10% of an organic solvent;
The photo-curing functional agent comprises a polymer monomer and a photo-initiator, wherein the mass ratio of the polymer monomer to the photo-initiator is 50-150:1, the polymer monomer is one or more selected from hydroxyethyl acrylate, trimethylolpropane triacrylate, polyethylene glycol methacrylate, polyethylene glycol diacrylate, methoxy polyethylene glycol methacrylate, epoxycyclohexane, ethoxylated trimethylpropane triacrylate, methacrylate and hexanediol diacrylate, and the photo-initiator is one or more selected from trimethylbenzoyl-diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-dimethylolpropionic acid and xylene ketone.
2. The method for preparing a solid lithium ion battery by 3D printing according to claim 1, wherein the positive electrode active material is selected from one or more of lithium cobaltate, lithium iron phosphate, lithium manganate, nickel cobalt manganese ternary, nickel cobalt aluminum material and manganese-based lithium-rich material, the conductive agent is selected from one or more of conductive carbon black, conductive graphite, carbon nano tube, acetylene black, graphene and carbon fiber, and the dispersing agent is selected from one or more of polyacrylic acid, acetonitrile, N-methylpyrrolidone, dimethylacetamide, ethanol, glycerol, ethylene carbonate and propylene carbonate.
3. The method for preparing a solid lithium ion battery according to claim 1, wherein the negative electrode active material is selected from one or more of graphite, silicon carbon and lithium titanate, the conductive agent is selected from one or more of conductive carbon black, conductive graphite, carbon nanotubes, acetylene black, graphene and carbon fiber, and the dispersing agent is selected from one or more of polyacrylic acid, acetonitrile, N-methylpyrrolidone, dimethylacetamide, ethanol, glycerol, ethylene carbonate and propylene carbonate.
4. The method for preparing a solid lithium ion battery by 3D printing according to claim 1, wherein the polymer in the composite electrolyte ink is selected from one or more of polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, polyvinylidene fluoride, polyvinyl chloride, polyvinyl alcohol, polyethyl acetate, polyethylene glycol divinyl ether, polycaprolactone, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium difluorosulfonimide, lithium tetrafluoroborate, lithium perchlorate, lithium bisoxalato borate, lithium hexafluoroarsonate, lithium dioxaoxalato borate, lithium trifluoromethane sulfonate and lithium bistrifluoromethylsulfonyi mide, the ion conductive powder is selected from one or more of lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, and the organic solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, methyl formate, dimethoxymethane, ethylene carbonate, and propylene carbonate.
5. The method for manufacturing a solid state lithium ion battery using 3D printing according to any one of claims 1 to 4, wherein the light source used for the light curing is in a wavelength range of 100nm to 500nm and an intensity of 1000mW/cm 2-4000mW/cm2 when the light curing is performed.
6. The method for manufacturing a solid state lithium ion battery using 3D printing according to claim 5, wherein in S2, a heating pad is placed under the glass substrate, the glass substrate is heated by the heating pad to dry the positive electrode on the glass substrate, and the heating temperature of the heating pad is 35 ℃ to 200 ℃.
7. A solid state lithium ion battery, characterized in that it is produced by the method according to any one of the preceding claims 1-6.
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