CN104409690A - Method for preparing lithium ion battery stacked vertical crossed electrode based on 3D printing technology - Google Patents

Method for preparing lithium ion battery stacked vertical crossed electrode based on 3D printing technology Download PDF

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CN104409690A
CN104409690A CN201410237597.1A CN201410237597A CN104409690A CN 104409690 A CN104409690 A CN 104409690A CN 201410237597 A CN201410237597 A CN 201410237597A CN 104409690 A CN104409690 A CN 104409690A
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lithium ion
ion battery
electrode
square crossing
anode
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CN104409690B (en
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杨尊先
郭太良
吕军
胡海龙
徐胜
严文焕
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Fuzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a method for preparing a lithium ion battery stacked vertical crossed electrode based on a 3D printing technology. The method mainly contains the following steps: lithium titanate, polyimide and lithium iron phosphate are respectively dissolved in respective solutions so as to prepare each electrode printing ink; and then, by a 3D printing technology, the stacked vertical crossed electrode structure is prepared by using lithium titanate as an anode material, polyimide as a diaphragm and lithium iron phosphate as a cathode material. The method for preparing the lithium ion battery stacked vertical crossed electrode mainly based on the 3D printing technology has characteristics of novel preparation method and simple technology. The prepared electrode material has advantages of large specific surface area, high energy density, small cathode and anode electrode spacing and the like. Diffusion velocity of lithium ion among the electrode is greatly improved so as to further raise ionic and electronic conductivity. The method provided by the invention has a huge application potential in the field of high-performance lithium ion batteries.

Description

A kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique
Technical field
The invention belongs to the combination of 3D technology and new forms of energy nm regime, relate generally to a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique.
Background technology
Along with the exhaustion day by day of traditional energy, lithium rechargeable battery represents as new forms of energy thus receives and pays close attention to widely.Simultaneously lithium ion battery is as the main power source of mobile communication equipment with mancarried electronic aid, has the advantages such as output voltage is higher, without memory, high-energy-density and become the focus studied both at home and abroad due to it.But the problem such as tradition is not high based on the lithium ion battery ubiquity specific area of plane electrode, energy storage density is limited, electrode polarization is serious.
In recent years along with the rise of nanometer technology and 3D printing technique, nanometer technology and 3D printing technique are extended to military affairs, electronics, medical science, biological, the fields such as new forms of energy, especially novel 3D prints the appearance of integrated lithium ion battery, effectively achieve the effective integration of lithium ion battery anode and cathode and package system thereof, revolutionize conventional planar electrode type lithium ion battery structure, this will substantially increase the ratio of active material in battery electrode material, shorten the migration distance in lithium ion charge and discharge process, thus substantially increase lithium ion diffusion rate and mobility.
But, existingly generally adopt anode and cathode interdigital structure based on the lithium ion battery prepared by 3D printing technique, print although this structure is easy to realize 3D, but because lithium ion battery electrode material change in volume in lithium storing process is remarkable and stress is larger, this interdigital structure electrode is easily deformable in its charge and discharge process even to cave in, cause anode and cathode short circuit, open circuit or formation to electrocute block, finally cause that cycle performance is deteriorated, the decay of lithium memory capacity is fast etc.
Summary of the invention
For shortcomings and deficiencies of the prior art, the invention provides a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique.This method is mainly dissolved in respective solution prepares each printing electrode ink with lithium titanate, polyimides, LiFePO4 respectively, recycling 3D printing technique, prepare with lithium titanate is anode material, polyimides is barrier film, and LiFePO4 is the lamination square crossing electrode structure of cathode material.Electrode material prepared by the method has the advantages such as specific area is large, energy density is high, anode and cathode electrode spacing is little.These all will greatly improve lithium ion diffusion velocity in-between the electrodes, and then improve its ion and electronic conductivity, meanwhile, the existence due to crossed electrode makes the Stability Analysis of Structures of battery, therefore, huge application potential is had in high performance lithium ion battery field.
For achieving the above object, the present invention adopts following technical scheme:
Prepare a method for lithium ion battery lamination square crossing electrode based on 3D printing technique, it is characterized in that: to utilize 3D printing technique to print with lithium titanate be anode material, be barrier film with polyimides, take LiFePO4 as the electrode structure of cathode material square crossing.
Wherein, described preparation method comprises the following steps:
1) lithium titanate and LiFePO4 are dissolved in deionized water and ethylene glycol respectively form the first mixed solution and the second mixed solution; Polyimides is dissolved in 1-METHYLPYRROLIDONE, polyethylene glycol, LiCl, polymethyl methacrylate mixed liquor and forms the 3rd mixed solution;
2) by centrifugal treating after above-mentioned three kinds of solution respectively ball milling;
3) three kinds of materials of gained after above-mentioned filtration are distributed to respectively in the solution of glycerol, hydroxypropyl cellulose, hydroxyethylcellulose and deionized water mixing;
4) get specification be the sheet glass of 16 × 8mm as substrate, utilize mask plate hide evaporation coating techniques prepare graphical gold electrode at glass substrate surface, respectively as cell cathode and anode current collector;
5) to utilize micro-nozzle to print at glass substrate surface with lithium titanate be anode material, with the square crossing electrode of lithiated-iron-phosphate cathode material, and print one deck between anodic-cathodic respectively with the barrier film of polyimides, prints corresponding contact conductor simultaneously;
6) glass substrate of printed square crossing electrode material is placed in tube furnace to heat-treat;
7) after utilizing poly methyl methacrylate plastic plate and dimethyl silicone polymer fluid sealant coaxial electrode material surrounding to be impaled along glass substrate; transfer in glove box; electrolyte is instilled under argon shield; to cover above it with poly methyl methacrylate plastic plate and dimethyl silicone polymer fluid sealant and seal again after complete wetting, namely obtaining the lithium ion battery of anode and cathode square crossing.
First Micro-Nozzles is utilized first to print one deck anode material in interval on a glass substrate from anode current collector district, one deck barrier film is printed in the same way again on anode material, and then print cathode material in the direction vertical with printed anode material from cathode collector district, one deck diaphragm material is printed in the same way more afterwards on cathode material, then repeat above-mentioned printing step, terminate until print.
In step 1): the first mixed solution is that 2-5g LiFePO4 dissolves in 110-150ml deionized water and 50-80ml ethylene glycol; Second mixed solution is that 5-10g lithium titanate is dissolved in the mixed solution of 1-3g polymethyl methacrylate, 100-200ml deionized water and 50-80ml ethylene glycol; 3rd mixed solution is that polyimides is dissolved in the mixed liquor of 1-METHYLPYRROLIDONE, polyethylene glycol, LiCl, polymethyl methacrylate, and the mass fraction of each material is respectively 75-85%N-methyl pyrrolidone, 10-20% polyethylene glycol, 1-5% LiCl and 10-20% polymethyl methacrylate.
Step 2) in: concrete technology condition is: after ball milling 24-48h, transfer in centrifuge, filter after processing 5-10min under 3500-4500rmp and remove large particulate matter, again filtrate is transferred in centrifuge subsequently and filter after centrifugal treating 3-5h under 3000-4000rmp.
Be strong stirring 1-3h in material dispersing technology condition in step 3).
Described cell cathode and anode current collector, its position is positioned at glass substrate two ends, and its length is 2-3mm, and width is 8mm.The electrode material of printed lamination square crossing is placed in tube furnace and is heated to 50-150 oc, keeps 1-3h.
The present invention mainly prepares the method for lithium ion battery lamination square crossing electrode based on 3D printing technique, have preparation method's novelty, the simple feature of technique; Prepared electrode material has the advantages such as specific area is large, energy density is high, anode and cathode electrode spacing is little.These all by greatly improve lithium ion in-between the electrodes diffusion velocity, and then improve its ion and electronic conductivity, have huge application potential in high performance lithium ion battery field.
Accompanying drawing explanation
Fig. 1 is the structural representation of one deck electrode material of printing of 3D printing technique and one deck barrier film.
Fig. 2 is the structural representation of a whole set of material (anode, barrier film, negative electrode, barrier film) that 3D printing technique prints.
Fig. 3 is cell electrode structure (the not adding electrode pole lead-in wire) structural representation that 3D printing technique prints.
Fig. 4 is cell electrode structure (the adding electrode pole lead-in wire) structural representation that 3D printing technique prints.
Embodiment
The present invention aims to provide a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique, existing by reference to the accompanying drawings and concrete execution mode illustrate
A kind of concrete steps preparing the method for lithium ion battery lamination square crossing electrode based on 3D printing technique are:
Embodiment 1
1) taking 2g LiFePO4 is added in the mixed solution of 110ml deionized water and 30ml ethylene glycol; Taking 5g lithium titanate is added in the mixed solution of 100ml deionized water, 50ml ethylene glycol and 1g PMMA; Take 1.5g Kynoar to dissolve in 80ml and be dissolved with 1-METHYLPYRROLIDONE (75wt%), polyethylene glycol (15wt%), LiCl(2%) and mixed solution PMMA(8%) in;
2) above-mentioned three kinds are transferred in ball mill, transfer to after ball milling 24h in centrifuge tube, be placed in centrifuge, filter after processing 5min under 3500rmp, transfer to again in centrifuge tube afterwards, be placed under centrifuge 3000rmp and filter after centrifugal treating 3h;
3) LiFePO4 of gained after above-mentioned filtration, Kynoar, lithium titanate be distributed to respectively and be dissolved with in solution that glycerol, HPC, HEC and deionized water make strong stirring 1.5h to dissolution homogeneity, the mass fraction of glycerol in gained solution, HPC, HEC and deionized water is respectively 25%, 7%, 0.8% and 15%;
4) get specification be the sheet glass of 16 × 8mm as substrate, utilize mask plate hide evaporation coating techniques prepare graphical gold electrode at glass substrate surface, respectively as cell cathode and anode current collector;
5) to utilize micro-nozzle to print at glass substrate surface with lithium titanate be anode material, with the square crossing electrode of lithiated-iron-phosphate cathode material, print corresponding contact conductor simultaneously.Fig. 1 is the structural representation of one deck electrode material and barrier film, one deck electrode structure schematic diagram that Fig. 2 is anode, barrier film, negative electrode intersect, and wherein 1 represent anode, 2 represent barrier film, and 3 represent negative electrode;
6) glass substrate of printed coaxial electrode material to be placed under tube furnace argon shield 50 oc heat treatment 1h;
7) after utilizing PMMA plastic plate and PDMS fluid sealant glass substrate surrounding to be impaled along glass substrate; transferred in glove box; electrolyte (EC:DEC=1:1) is instilled under argon shield; to cover above it with PMMA plastic plate and PDMS fluid sealant and seal again after complete wetting; namely the coaxial lithium ion battery of anode and cathode is formed; Fig. 4 is the lithium ion battery structure schematic diagram of the lithium titanate/LiFePO4 anode and cathode square crossing after encapsulation, and 4 represent anode current collector, and 5 represent cathode collector.
 
Embodiment 2
1) taking 3g LiFePO4 is added in the mixed solution of 120ml deionized water and 70ml ethylene glycol; Taking 7g lithium titanate is added in the mixed solution of 150ml deionized water, 60ml ethylene glycol and 2g PMMA; Take 1.5g Kynoar to dissolve in 80ml and be dissolved with 1-METHYLPYRROLIDONE (75wt%), polyethylene glycol (15wt%), LiCl(2%) and mixed solution PMMA(8%) in;
2) above-mentioned three kinds are transferred in ball mill, transfer to after ball milling 36h in centrifuge tube, be placed in centrifuge, filter after processing 8min under 4000rmp, transfer to again in centrifuge tube afterwards, be placed under centrifuge 3500rmp and filter after centrifugal treating 4h;
3) LiFePO4 of gained after above-mentioned filtration, Kynoar, lithium titanate be distributed to respectively and be dissolved with in solution that glycerol, HPC, HEC and deionized water make strong stirring 2h to dissolution homogeneity, the mass fraction of glycerol in gained solution, HPC, HEC and deionized water is respectively 25%, 7%, 0.8% and 15%;
4) get specification be the sheet glass of 16 × 8mm as substrate, utilize mask plate hide evaporation coating techniques prepare graphical gold electrode at glass substrate surface, respectively as cell cathode and anode current collector;
5) to utilize micro-nozzle to print at glass substrate surface with lithium titanate be anode material, with the square crossing electrode of lithiated-iron-phosphate cathode material, print corresponding contact conductor simultaneously.Fig. 1 is the structural representation of one deck electrode material and barrier film, one deck electrode structure schematic diagram that Fig. 2 is anode, barrier film, negative electrode intersect, and wherein 1 represent anode, 2 represent barrier film, and 3 represent negative electrode;
6) glass substrate of printed coaxial electrode material to be placed under tube furnace argon shield 50 oc heat treatment 1h;
7) after utilizing PMMA plastic plate and PDMS fluid sealant glass substrate surrounding to be impaled along glass substrate; transferred in glove box; electrolyte (EC:DEC=1:1.5) is instilled under argon shield; to cover above it with PMMA plastic plate and PDMS fluid sealant and seal again after complete wetting; namely the coaxial lithium ion battery of anode and cathode is formed; Fig. 4 is the lithium ion battery structure schematic diagram of the lithium titanate/LiFePO4 anode and cathode square crossing after encapsulation; 4 represent anode current collector, and 5 represent cathode collector.
 
Embodiment 3
1) taking 5g LiFePO4 is added in the mixed solution of 150ml deionized water and 80ml ethylene glycol; Taking 10g lithium titanate is added in the mixed solution of 200ml deionized water, 80ml ethylene glycol and 3g PMMA; Take 1.5g Kynoar to dissolve in 80ml and be dissolved with 1-METHYLPYRROLIDONE (75wt%), polyethylene glycol (15wt%), LiCl(2%) and mixed solution PMMA(8%) in;
2) above-mentioned three kinds are transferred in ball mill, transfer to after ball milling 48h in centrifuge tube, be placed in centrifuge, filter after processing 10min under 4500rmp, transfer to again in centrifuge tube afterwards, be placed under centrifuge 4000rmp and filter after centrifugal treating 5h;
3) LiFePO4 of gained after above-mentioned filtration, Kynoar, lithium titanate be distributed to respectively and be dissolved with in solution that glycerol, HPC, HEC and deionized water make strong stirring 3h to dissolution homogeneity, the mass fraction of glycerol in gained solution, HPC, HEC and deionized water is respectively 25%, 7%, 0.8% and 15%;
4) get specification be the sheet glass of 16 × 8mm as substrate, utilize mask plate hide evaporation coating techniques prepare graphical gold electrode at glass substrate surface, respectively as cell cathode and anode current collector;
5) to utilize micro-nozzle to print at glass substrate surface with lithium titanate be anode material, with the square crossing electrode of lithiated-iron-phosphate cathode material, print corresponding contact conductor simultaneously, Fig. 1 is the structural representation of one deck electrode material and barrier film, one deck electrode structure schematic diagram that Fig. 2 is anode, barrier film, negative electrode intersect, wherein 1 represent anode, 2 represent barrier film, and 3 represent negative electrode;
6) glass substrate of printed coaxial electrode material to be placed under tube furnace argon shield 50 oc heat treatment 1h;
7) after utilizing PMMA plastic plate and PDMS fluid sealant glass substrate surrounding to be impaled along glass substrate; transferred in glove box; electrolyte (EC:DEC=2:1) is instilled under argon shield; to cover above it with PMMA plastic plate and PDMS fluid sealant and seal again after complete wetting; namely the coaxial lithium ion battery of anode and cathode is formed; Fig. 4 is the lithium ion battery structure schematic diagram of the lithium titanate/LiFePO4 anode and cathode square crossing after encapsulation, and 4 represent anode current collector, and 5 represent cathode collector.

Claims (8)

1. prepare a method for lithium ion battery lamination square crossing electrode based on 3D printing technique, it is characterized in that: to utilize 3D printing technique to print with lithium titanate be anode material, be barrier film with polyimides, take LiFePO4 as the electrode structure of cathode material square crossing.
2. a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique according to claim 1, is characterized in that: described preparation method comprises the following steps:
1) lithium titanate and LiFePO4 are dissolved in deionized water and ethylene glycol respectively form the first mixed solution and the second mixed solution; Polyimides is dissolved in 1-METHYLPYRROLIDONE, polyethylene glycol, LiCl, polymethyl methacrylate mixed liquor and forms the 3rd mixed solution;
2) by centrifugal treating after above-mentioned three kinds of solution respectively ball milling;
3) three kinds of materials of gained after above-mentioned filtration are distributed to respectively in the solution of glycerol, hydroxypropyl cellulose, hydroxyethylcellulose and deionized water mixing;
4) get specification be the sheet glass of 16 × 8mm as substrate, utilize mask plate hide evaporation coating techniques prepare graphical gold electrode at glass substrate surface, respectively as cell cathode and anode current collector;
5) to utilize micro-nozzle to print at glass substrate surface with lithium titanate be anode material, with the square crossing electrode of lithiated-iron-phosphate cathode material, and print one deck between anodic-cathodic respectively with the barrier film of polyimides, prints corresponding contact conductor simultaneously;
6) glass substrate of printed square crossing electrode material is placed in tube furnace to heat-treat;
7) after utilizing poly methyl methacrylate plastic plate and dimethyl silicone polymer fluid sealant coaxial electrode material surrounding to be impaled along glass substrate; transfer in glove box; electrolyte is instilled under argon shield; to cover above it with poly methyl methacrylate plastic plate and dimethyl silicone polymer fluid sealant and seal again after complete wetting, namely obtaining the lithium ion battery of anode and cathode square crossing.
3. a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique according to claim 1, it is characterized in that: first utilize Micro-Nozzles first to print one deck anode material in interval on a glass substrate from anode current collector district, one deck barrier film is printed in the same way again on anode material, and then print cathode material in the direction vertical with printed anode material from cathode collector district, one deck diaphragm material is printed in the same way more afterwards on cathode material, then repeat above-mentioned printing step, terminate until print.
4. a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique according to claim 2, is characterized in that: in step 1): the first mixed solution is that 2-5g LiFePO4 dissolves in 110-150ml deionized water and 50-80ml ethylene glycol; Second mixed solution is that 5-10g lithium titanate is dissolved in the mixed solution of 1-3g polymethyl methacrylate, 100-200ml deionized water and 50-80ml ethylene glycol; 3rd mixed solution is that polyimides is dissolved in the mixed liquor of 1-METHYLPYRROLIDONE, polyethylene glycol, LiCl, polymethyl methacrylate, and the mass fraction of each material is respectively 75-85%N-methyl pyrrolidone, 10-20% polyethylene glycol, 1-5% LiCl and 10-20% polymethyl methacrylate.
5. a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique according to claim 2, it is characterized in that: step 2) in: concrete technology condition is: after ball milling 24-48h, transfer in centrifuge, filter after processing 5-10min under 3500-4500rmp and remove large particulate matter, again filtrate is transferred in centrifuge subsequently and filter after centrifugal treating 3-5h under 3000-4000rmp.
6. a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique according to claim 2, is characterized in that: be strong stirring 1-3h in material dispersing technology condition in step 3).
7. a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique according to claim 2, it is characterized in that: described cell cathode and anode current collector, its position is positioned at glass substrate two ends, and its length is 2-3mm, and width is 8mm.
8. a kind of method preparing lithium ion battery lamination square crossing electrode based on 3D printing technique according to claim 2, is characterized in that: the electrode material of printed lamination square crossing is placed in tube furnace and is heated to 50-150 oc, keeps 1-3h.
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Cited By (3)

* Cited by examiner, † Cited by third party
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WO2019012012A1 (en) * 2017-07-11 2019-01-17 University College Cork - National University Of Ireland, Cork 3d printed battery and method of making same
CN109659631A (en) * 2018-11-28 2019-04-19 孟婷婷 Ultra-thin lead-acid storage battery polar plate clusters module
CN113306320A (en) * 2021-05-19 2021-08-27 东北大学 Solar cell metal grid spray printing forming method and device for laser in-situ film opening

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EP1678772A4 (en) * 2003-10-14 2010-06-02 Univ Tel Aviv Future Tech Dev Three-dimensional thin-film microbattery
CN101421866A (en) * 2004-02-11 2009-04-29 加州大学评议会 High aspect ratio C-MEMS architecture
CN101427415A (en) * 2004-04-27 2009-05-06 特拉维夫大学未来技术研发有限公司 3-D microbatteries based on interlaced micro-container structures
CN101030655B (en) * 2007-04-04 2010-07-07 天津大学 Micro-battery structure and its production

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Publication number Priority date Publication date Assignee Title
WO2019012012A1 (en) * 2017-07-11 2019-01-17 University College Cork - National University Of Ireland, Cork 3d printed battery and method of making same
CN109659631A (en) * 2018-11-28 2019-04-19 孟婷婷 Ultra-thin lead-acid storage battery polar plate clusters module
CN113306320A (en) * 2021-05-19 2021-08-27 东北大学 Solar cell metal grid spray printing forming method and device for laser in-situ film opening
CN113306320B (en) * 2021-05-19 2022-06-17 东北大学 Solar cell metal grid spray printing forming method and device for laser in-situ film opening

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