CN104409774B - 3D printing method of lithium battery - Google Patents

3D printing method of lithium battery Download PDF

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Publication number
CN104409774B
CN104409774B CN201410237589.7A CN201410237589A CN104409774B CN 104409774 B CN104409774 B CN 104409774B CN 201410237589 A CN201410237589 A CN 201410237589A CN 104409774 B CN104409774 B CN 104409774B
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slurry
anode
cathode
layer
barrier film
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CN104409774A (en
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杨尊先
郭太良
严文焕
胡海龙
徐胜
吕军
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Fuzhou University
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Fuzhou University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a 3D printing method of a lithium battery. The method comprises the following steps: firstly, positive and negative slurry and diaphragm slurry required for 3D printing are prepared; secondly, each slurry is respectively printed into positive and negative electrodes of a lithium battery and an electrode diaphragm layer positioned between the positive and negative electrodes; thirdly, under the protection of argon in a test-tube furnace, heat treatment is carried out to prepare an annular electrode composite material assembled by overlapping the positive electrode, the diaphragm layer and the negative electrode; and finally, the annular electrode composite material is transferred into a glove box for packaging so as to obtain an annular lithium ion battery formed by successively overlapping the cathode, the diaphragm and the anode. The preparation method is novel, and the technology is simple, accurate and controllable. The prepared material has a special structure formed by successively overlapping the cathode, the diaphragm and the anode and has large specific surface area. Each cathode, diaphragm and anode annular material itself forms a miniature lithium ion battery. Diffusion distance of lithium ion in the material is shortened greatly, and corresponding diffusion velocity is improved. The lithium ion battery has high ionic and electronic conductivity.

Description

A kind of 3D Method of printing of lithium battery
Technical field
The present invention relates to the 3D Method of printing of a kind of lithium battery, belong to nanometer energy storage material field.
Background technology
Along with the exhaustion day by day of traditional energy, lithium rechargeable battery represents thus of great interest as new forms of energy.Lithium ion battery is as the main power source of mobile communication equipment Yu mancarried electronic aid simultaneously, has the advantages such as higher, without memory, the high-energy-density of output voltage due to it and becomes the focus of research both at home and abroad.But generally there is the problems such as specific surface area is the highest, energy storage density is limited, electrode polarization is serious in tradition lithium ion battery based on plane electrode.
Recently as nanotechnology and the rise of 3D printing technique, nanotechnology and 3D printing technique have been extended to military affairs, electronics, medical science, biological, the fields such as new forms of energy, the most 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 substance 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, existing typically use anode and cathode interdigital structure based on the lithium ion battery prepared by 3D printing technique, although this structure is easily achieved 3D and prints, but due to lithium ion battery electrode material, in lithium storing process, change in volume is notable and stress is bigger, 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, ultimately cause that cycle performance is deteriorated, the decay of lithium memory capacity is fast.Based on other structure lithium ion battery prepared by 3D printing technique, the problem still suffering from the many aspects such as positive and negative pole material isolation, printing type selection at present.
Summary of the invention
For shortcomings and deficiencies of the prior art, the invention provides a kind of annular preparation method of lithium ion battery overlapped successively based on 3D printing technique negative electrode, barrier film and anode.First the inventive method specifically includes for preparing the positive and negative electrode slurry needed for 3D prints and barrier film slurry thereof;Each slurry printed respectively the positive and negative electrode of lithium battery again and is positioned at above-mentioned electrode diaphragm layer between the two, subsequently, through Overheating Treatment, packaging technology, finally giving the annular lithium ion battery that negative electrode, barrier film and anode overlap successively.The present invention prepares, based on 3D printing technique, the annular lithium ion battery that negative electrode, barrier film and anode overlap successively, there is preparation method novel, technique is simple, and controllable precise, prepared material has specific cathode, barrier film and anode and overlaps distributed architecture, big specific surface area successively;Each negative electrode, barrier film and anode annulus material one miniature lithium ion battery of composition itself, this will substantially reduce lithium ion diffusion length in the material, improve corresponding diffusion velocity, there is higher ion and electronic conductivity, have huge application potential in high performance lithium ion battery field.
For achieving the above object, the present invention adopts the following technical scheme that
The 3D Method of printing of a kind of lithium battery, utilizes 3D printing technique to print the lamination circular ring electrode structure with lithium titanate as anode material, with polyimides as barrier film, with LiFePO4 as cathode material.Subsequently; the lamination annular composite with lithium titanate as anode material, with polyimides as barrier film, with LiFePO4 as cathode material is obtained after heat treatment under argon shield; then, it is packaged in transferring to glove box, finally gives lamination circular ring electrode lithium ion battery.
Preparation method of the present invention comprises the steps:
A kind of 3D Method of printing of lithium battery, its preparation method comprises the following steps:
(1) the cathode and anode slurry needed for 3D prints is prepared;
(2) barrier film slurry is prepared;
(3) by prepared slurry, with 30 μm shower nozzles, under 600psi pressure, print the yin, yang electrode of lithium battery respectively with 250 μm/s and be positioned at above-mentioned electrode diaphragm between the two;
(4) after printed, in argon gas shielded adapts to tube furnace, anneal under 600 degree of hot conditionss 2h, makes electrode, barrier film solidify;
(5) after electrode, barrier film make, with cut thin-walled methyl methacrylate, put into the battery structure prepared, major part space is sealed with PolyDiMethylSiloxane gel, solidify at a temperature of 150 degree, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra polydimethylsiloxane.
Described positive and negative electrode and barrier film slurry produce as follows:
(1) take the highly enriched lithium titanate 4-5g that weight ratio is 57% to be dispersed in the deionized water of 140-160ml and the sodium lauryl sulphate of 9-14g and form the first mixed solution;Separately take the LiFePO4 2-4g of 60% to be scattered in the sodium lauryl sulphate of 110-130 ml deionized water and 9-14g and form the second mixed solution;
(2) impregnate 40-50 hour under the first mixed solution obtained and the second mixed solution room temperature respectively, and be centrifuged 2-3 hour under 4000rpm, collect Grain size controlling at a diameter of 170-190nm, the solid obtained is dispersed back into glycerol respectively, carboxymethyl starch sodium, in the 3rd mixed solution that polyvinyl pyrrolidone homopolymer and sodium carboxymethyl cellulose are formed, and ultrasonic 2-3h, thus respectively obtain the first slurry and the second slurry, wherein glycerol in the 3rd mixed solution, carboxymethyl starch sodium, in polyvinyl pyrrolidone homopolymer and sodium carboxymethyl cellulose, each Ingredient percent is respectively 10-13%, 4-8%, 3-5% and 3-5%;
(3) the first slurry obtained, the i.e. composition of lithium titanate slurry are 20-29% glycerol, 20-30% sodium lauryl sulphate, 7-11% carboxymethyl starch sodium, 3-5% polyvinyl pyrrolidone homopolymer, the sodium carboxymethyl cellulose of 2-3% and deionized water, as cathode of lithium battery slurry;Being obtained the second slurry i.e. composition of LiFePO4 slurry is 20-30% glycerol, 20-30% sodium lauryl sulphate, 7-9% carboxymethyl starch sodium, 2-3% sodium carboxymethyl cellulose, 3-5% polyvinyl pyrrolidone homopolymer and deionized water, as lithium battery anode slurry;
(4) subsequently, the first slurry and the second slurry the most at room temperature solvent flashing until in slurry solid masses be advisable than during for 55-65%, finally prepare in order to 3D lithium battery print anode and cathode slurry;
(5) polyimide diaphragm material preparation process: under the conditions of-3 DEG C, is 1mol.L by 5-10ml concentration-1Pyromellitic acid dianhydride and 5-10ml concentration be 1mol.L-14, the N,N-dimethylacetamide of 4'-diaminodiphenyl ether and equimolar quality thereof carries out polycondensation reaction and generates polyamic acid, thus obtains the original polyamic acid solution of solids content with 15%;At a temperature of 60 DEG C after dried overnight, it is heated to 100-300 DEG C with 3 DEG C/min, it is achieved hot imidization;Then it is incorporated in 110-130ml deionized water and 30-50ml ethylene glycol mixed solution, at room temperature after dipping 24h, take out precipitate, again precipitate is further distributed in the mixed solution that the glycerol of 10-13%, the hydroxypropyl cellulose of 3-5% and 3-4% water hydroxyethyl cellulose are formed, finally prepare the glycerol that polyimides paste composition is 20-30%, the ethylene glycol of 20-30%, the hydroxypropyl cellulose of 7-10%, the hydroxyethyl cellulose of 2-4% and deionized water, prepare its barrier film slurry.
Constituting if described septation and positive and negative electrode are respectively dried layer circular array, described barrier film is between positive and negative electrode layer, and the unification of its concrete printing step is:
(1) the upper semi-circle part above plane ring shaped array is printed;
(2) the right semi-circle part of plane ring shaped array right is printed;
(3) the lower half circle part below plane ring shaped array is printed;
(4) second half circular portion of lower half circle below circular array plane is printed;
(5) printing step (4) molded annular lower half circle part adjacent and above;
(6) second half circular portion of printing step (5) molded lower half circle part;
(7) continue from molded annulus, to print its lower half circle adjacent and above and second half circular portion, until another semicircle completing step (1) upper semi-circle part only prints to;
(8), after completing the printing of a type circle ring array layer, the printing of next type circle ring array layer is continued.
(9) in battery electrode lead portion, all of cathode material annulus battery metal to be covered negative electrode, all of anode material annulus layer requires to cover battery metal anode;Simultaneously in order to be effectively isolated each anode and cathode electrode layer, membrane layer annulus layer to be completely covered beyond corresponding anode and cathode electrode respectively, i.e. on metal anode limit, and barrier film annulus front layer to be exceeded cathode ring layer, and on metallic cathode limit, barrier film annulus front layer to be exceeded anode annulus layer.
The present invention prepares, based on 3D printing technique, the annular lithium ion battery that negative electrode, barrier film and anode overlap successively, preparation method is novel, technique is simple, and controllable precise, prepared material has specific cathode, barrier film and anode and overlaps distributed architecture, big specific surface area successively;Each negative electrode, barrier film and anode annulus material one miniature lithium ion battery of composition itself, this will substantially reduce lithium ion diffusion length in the material, improve corresponding diffusion velocity, there is higher ion and electronic conductivity, have huge application potential in high performance lithium ion battery field.
Accompanying drawing explanation
The printing step figure that Fig. 1-4 embodiment of the present invention annulus material is concrete.
The annulus material structure figure printed under Fig. 5 embodiment of the present invention.
The lithium battery interior part-structure that Fig. 6 embodiment of the present invention circular ring type file printing goes out.
Detailed description of the invention
It is desirable to provide the 3D Method of printing of a kind of lithium battery, illustrate in conjunction with accompanying drawing and specific embodiment.
Embodiment 1
1) take the highly enriched lithium titanate 4g that weight ratio is 57% to be dispersed in the deionized water of 140ml and the sodium lauryl sulphate of 9g and form the first mixed solution;Separately take the LiFePO4 2g that weight ratio is 60% to be scattered in the sodium lauryl sulphate of 110ml deionized water and 9g and form the second mixed solution;
2) by the first mixed solution and the second mixed solution the most at room temperature dipping 40 hours, it is centrifuged 2 hours under 4000rpm, the Grain size controlling gathered is at a diameter of 170nm, the granule collected is dispersed back into glycerol that weight ratio is 10% respectively, weight ratio is 4% carboxymethyl starch sodium, weight ratio be 3% polyvinyl pyrrolidone homopolymer (PVP), weight ratio be in 3% sodium carboxymethyl cellulose, and it is ultrasonic to carry out 2h, thus produce homogenate, it is denoted as the first slurry and the second slurry respectively;
3) glycerol that lithium titanate homogenate is 20% prepared, the sodium lauryl sulphate of 20%, the carboxymethyl starch sodium of 7%, 3% polyvinyl pyrrolidone homopolymer (PVP), the sodium carboxymethyl cellulose of 2% and deionized water, as cathode of lithium battery slurry;The LiFePO4 homogenate prepared is 20% glycerol, the sodium lauryl sulphate of 20%, 7% carboxymethyl starch sodium, 2% sodium carboxymethyl cellulose, and 3% polyvinyl pyrrolidone homopolymer (PVP) and deionized water, as lithium battery anode slurry;
4) when being 55% by cathode of lithium battery slurry and anode sizing agent the most at room temperature solvent flashing to homogenate solid masses ratio, the final anode and cathode slurry obtained in order to the printing of 3D lithium battery;
5) polyimide diaphragm material preparation process: under the conditions of-3 DEG C, is 1mol.L by 5ml concentration-1Pyromellitic acid dianhydride (PMDA) and 5ml concentration be 1mol.L-14, the N,N-dimethylacetamide (DMAC) of 4'-diaminodiphenyl ether (ODA) and equimolar quality thereof carries out polycondensation reaction and generates polyamic acid (PAA), thus obtains the original PAA solution of solids content with 15%.At a temperature of 60 DEG C after dried overnight, it is heated to 100 DEG C with 3 DEG C/min, it is achieved hot imidization.Then it is incorporated in 110ml deionized water and 30ml ethylene glycol mixed solution, at room temperature after dipping 24h, take out precipitate, again precipitate is further distributed in the mixed solution that the glycerol of 10%, the hydroxypropyl cellulose of 3% and 3% water hydroxyethyl cellulose are formed, finally prepare the glycerol that polyimides paste composition is 20%, the ethylene glycol of 20%, the hydroxypropyl cellulose of 7%, the hydroxyethyl cellulose of 2% and deionized water, prepare its barrier film slurry.
6) before prepare slurry, use 30um shower nozzle, in 600psi(Pounds per square inch, pressure unit) under print with 250um/s.The unification of its concrete printing step is:
(1) the upper semi-circle part above plane ring shaped array is printed;
(2) the right semi-circle part of plane ring shaped array right is printed;
(3) the lower half circle part below plane ring shaped array is printed;
(4) second half circular portion of lower half circle below circular array plane is printed;
(5) printing step (4) molded annular lower half circle part adjacent and above;
(6) second half circular portion of printing step (5) molded lower half circle part;
(7) continue from molded annulus, to print its lower half circle adjacent and above and second half circular portion, until another semicircle completing step (1) upper semi-circle part only prints to;
(8), after completing the printing of a type circle ring array layer, the printing of next type circle ring array layer is continued.One layer of substantially figure such as Fig. 1-4 printed.Three-dimensionally shaped figure in reality is as shown in Figure 5.
(9) as shown in Figure 6, at battery electrode lead portion, all of cathode material annulus battery metal to be covered negative electrode, all of anode material annulus layer requires to cover battery metal anode.Simultaneously in order to be effectively isolated each anode and cathode electrode layer, membrane layer annulus layer to be completely covered beyond corresponding anode and cathode electrode respectively, i.e. on metal anode limit, and barrier film annulus front layer to be exceeded cathode ring layer, and on metallic cathode limit, barrier film annulus front layer to be exceeded anode annulus layer.
7) after printed, with under argon gas shielded in test tube stove, with 600 degree of high annealing 2h.So electrode, barrier film is prepared complete.
8) after electrode, barrier film make.By cut thin-walled methyl methacrylate (PMMA), put into the battery structure prepared, major part space is sealed with polydimethylsiloxane (PDMS) gel, solidify at a temperature of 150 degree, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra PDMS.
Embodiment 2
1) take the highly enriched lithium titanate 4.5g that weight ratio is 57% to be dispersed in the deionized water of 150ml and the sodium lauryl sulphate of 11g and form the first mixed solution;Separately take the LiFePO4 3g that weight ratio is 60% to be scattered in the sodium lauryl sulphate of 120ml deionized water and 11g and form the second mixed solution;
2) by the first mixed solution and the second mixed solution the most at room temperature dipping 45 hours, it is centrifuged 2.5 hours under 4000rpm, the Grain size controlling gathered is at a diameter of 180nm, the granule collected is dispersed back into glycerol that weight ratio is 12% respectively, weight ratio is 6% carboxymethyl starch sodium, weight ratio be 4% polyvinyl pyrrolidone homopolymer (PVP), weight ratio be in 4% sodium carboxymethyl cellulose, and it is ultrasonic to carry out 2.5h, thus produce homogenate, it is denoted as the first slurry and the second slurry respectively;
3) glycerol that lithium titanate homogenate is 25% prepared, the sodium lauryl sulphate of 25%, the carboxymethyl starch sodium of 9%, 4% polyvinyl pyrrolidone homopolymer (PVP), the sodium carboxymethyl cellulose of 2.5% and deionized water, as cathode of lithium battery slurry;The LiFePO4 homogenate prepared is 25% glycerol, the sodium lauryl sulphate of 25%, 8% carboxymethyl starch sodium, 2.5% sodium carboxymethyl cellulose, and 4% polyvinyl pyrrolidone homopolymer (PVP) and deionized water, as lithium battery anode slurry;
4) when being 60% by cathode of lithium battery slurry and anode sizing agent the most at room temperature solvent flashing to homogenate solid masses ratio, the final anode and cathode slurry obtained in order to the printing of 3D lithium battery;
5) polyimide diaphragm material preparation process: under the conditions of-3 DEG C, is 1mol.L by 7ml concentration-1Pyromellitic acid dianhydride (PMDA) and 7ml concentration be 1mol.L-14, the N,N-dimethylacetamide (DMAC) of 4'-diaminodiphenyl ether (ODA) and equimolar quality thereof carries out polycondensation reaction and generates polyamic acid (PAA), thus obtains the original PAA solution of solids content with 15%.At a temperature of 60 DEG C after dried overnight, it is heated to 200 DEG C with 3 DEG C/min, it is achieved hot imidization.Then it is incorporated in 120ml deionized water and 40ml ethylene glycol mixed solution, at room temperature after dipping 24h, take out precipitate, again precipitate is further distributed in the mixed solution that the glycerol of 12%, the hydroxypropyl cellulose of 4% and 3.5% water hydroxyethyl cellulose are formed, finally prepare the glycerol that polyimides paste composition is 25%, the ethylene glycol of 25%, the hydroxypropyl cellulose of 8%, the hydroxyethyl cellulose of 3% and deionized water, prepare its barrier film slurry.
6) before prepare slurry, use 30um shower nozzle, in 600psi(Pounds per square inch, pressure unit) under print with 250um/s.The unification of its concrete printing step is:
(1) the upper semi-circle part above plane ring shaped array is printed;
(2) the right semi-circle part of plane ring shaped array right is printed;
(3) the lower half circle part below plane ring shaped array is printed;
(4) second half circular portion of lower half circle below circular array plane is printed;
(5) printing step (4) molded annular lower half circle part adjacent and above;
(6) second half circular portion of printing step (5) molded lower half circle part;
(7) continue from molded annulus, to print its lower half circle adjacent and above and second half circular portion, until another semicircle completing step (1) upper semi-circle part only prints to;
(8), after completing the printing of a type circle ring array layer, the printing of next type circle ring array layer is continued.One layer of substantially figure such as Fig. 1-4 printed.Three-dimensionally shaped figure in reality is as shown in Figure 5.
(9) as shown in Figure 6, at battery electrode lead portion, all of cathode material annulus battery metal to be covered negative electrode, all of anode material annulus layer requires to cover battery metal anode.Simultaneously in order to be effectively isolated each anode and cathode electrode layer, membrane layer annulus layer to be completely covered beyond corresponding anode and cathode electrode respectively, i.e. on metal anode limit, and barrier film annulus front layer to be exceeded cathode ring layer, and on metallic cathode limit, barrier film annulus front layer to be exceeded anode annulus layer.
7) after printed, with under argon gas shielded in test tube stove, with 600 degree of high annealing 2h.So electrode, barrier film is prepared complete.
8) after electrode, barrier film make.By cut thin-walled methyl methacrylate (PMMA), put into the battery structure prepared, major part space is sealed with polydimethylsiloxane (PDMS) gel, solidify at a temperature of 150 degree, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra PDMS.
Embodiment 3
1) take the highly enriched lithium titanate 5g that weight ratio is 57% to be dispersed in the deionized water of 160ml and the sodium lauryl sulphate of 14g and form the first mixed solution;Separately take the LiFePO4 4g that weight ratio is 60% to be scattered in the sodium lauryl sulphate of 130ml deionized water and 14g and form the second mixed solution;
2) by the first mixed solution and the second mixed solution the most at room temperature dipping 50 hours, it is centrifuged 3 hours under 4000rpm, the Grain size controlling gathered is at a diameter of 190nm, the granule collected is dispersed back into glycerol that weight ratio is 13% respectively, weight ratio is 8% carboxymethyl starch sodium, weight ratio be 5% polyvinyl pyrrolidone homopolymer (PVP), weight ratio be in 5% sodium carboxymethyl cellulose, and it is ultrasonic to carry out 3h, thus produce homogenate, it is denoted as the first slurry and the second slurry respectively;
3) glycerol that lithium titanate homogenate is 29% prepared, the sodium lauryl sulphate of 30%, the carboxymethyl starch sodium of 11%, 5% polyvinyl pyrrolidone homopolymer (PVP), the sodium carboxymethyl cellulose of 3% and deionized water, as cathode of lithium battery slurry;The LiFePO4 homogenate prepared is 30% glycerol, the sodium lauryl sulphate of 30%, 9% carboxymethyl starch sodium, 3% sodium carboxymethyl cellulose, and 5% polyvinyl pyrrolidone homopolymer (PVP) and deionized water, as lithium battery anode slurry;
4) when being 65% by cathode of lithium battery slurry and anode sizing agent the most at room temperature solvent flashing to homogenate solid masses ratio, the final anode and cathode slurry obtained in order to the printing of 3D lithium battery;
5) polyimide diaphragm material preparation process: under the conditions of-3 DEG C, is 1mol.L by 10ml concentration-1Pyromellitic acid dianhydride (PMDA) and 10ml concentration be 1mol.L-14, the N,N-dimethylacetamide (DMAC) of 4'-diaminodiphenyl ether (ODA) and equimolar quality thereof carries out polycondensation reaction and generates polyamic acid (PAA), thus obtains the original PAA solution of solids content with 15%.At a temperature of 60 DEG C after dried overnight, it is heated to 300 DEG C with 3 DEG C/min, it is achieved hot imidization.Then it is incorporated in 130ml deionized water and 50ml ethylene glycol mixed solution, at room temperature after dipping 24h, take out precipitate, again precipitate is further distributed in the mixed solution that the glycerol of 13%, the hydroxypropyl cellulose of 5% and 4% water hydroxyethyl cellulose are formed, finally prepare the glycerol that polyimides paste composition is 30%, the ethylene glycol of 30%, the hydroxypropyl cellulose of 10%, the hydroxyethyl cellulose of 4% and deionized water, prepare its barrier film slurry.
6) before prepare slurry, use 30um shower nozzle, in 600psi(Pounds per square inch, pressure unit) under print with 250um/s.The unification of its concrete printing step is:
(1) the upper semi-circle part above plane ring shaped array is printed;
(2) the right semi-circle part of plane ring shaped array right is printed;
(3) the lower half circle part below plane ring shaped array is printed;
(4) second half circular portion of lower half circle below circular array plane is printed;
(5) printing step (4) molded annular lower half circle part adjacent and above;
(6) second half circular portion of printing step (5) molded lower half circle part;
(7) continue from molded annulus, to print its lower half circle adjacent and above and second half circular portion, until another semicircle completing step (1) upper semi-circle part only prints to;
(8), after completing the printing of a type circle ring array layer, the printing of next type circle ring array layer is continued.One layer of substantially figure such as Fig. 1-4 printed.Three-dimensionally shaped figure in reality is as shown in Figure 5.
(9) as shown in Figure 6, at battery electrode lead portion, all of cathode material annulus battery metal to be covered negative electrode, all of anode material annulus layer requires to cover battery metal anode.Simultaneously in order to be effectively isolated each anode and cathode electrode layer, membrane layer annulus layer to be completely covered beyond corresponding anode and cathode electrode respectively, i.e. on metal anode limit, and barrier film annulus front layer to be exceeded cathode ring layer, and on metallic cathode limit, barrier film annulus front layer to be exceeded anode annulus layer.
7) after printed, with under argon gas shielded in test tube stove, with 600 degree of high annealing 2h.So electrode, barrier film is prepared complete.
8) after electrode, barrier film make.By cut thin-walled methyl methacrylate (PMMA), put into the battery structure prepared, major part space is sealed with polydimethylsiloxane (PDMS) gel, solidify at a temperature of 150 degree, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra PDMS.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.

Claims (2)

1. the 3D Method of printing of a lithium battery, it is characterised in that: it is prepared as follows,
A () prepares the cathode and anode slurry needed for 3D prints;
B () prepares barrier film slurry;
C (), by prepared slurry, with 30 μm shower nozzles, prints the cathode and anode of lithium battery respectively with 250 μm/s under 600psi pressure and is positioned at barrier film between the two;Constituting if barrier film and cathode and anode are respectively dried layer circular array, its concrete printing step is:
(1) the upper semi-circle part above plane ring shaped array is printed;
(2) the right semi-circle part of plane ring shaped array right is printed;
(3) the lower half circle part below plane ring shaped array is printed;
(4) second half circular portion of lower half circle below circular array plane is printed;
(5) printing step (4) molded annular lower half circle part adjacent and above;
(6) second half circular portion of printing step (5) molded lower half circle part;
(7) continue from molded annulus, to print its lower half circle adjacent and above and second half circular portion, until another semicircle completing step (1) upper semi-circle part only prints to;
(8), after completing the printing of a type circle ring array layer, the printing of next type circle ring array layer is continued;
(9) in battery electrode lead portion, all of cathode material annulus layer battery metal to be covered cathode current collector, all of anode material annulus layer battery metal to be covered anode current collector;Simultaneously in order to be effectively isolated each cathode and anode annulus layer, barrier film annulus layer to be completely covered beyond corresponding cathode and anode annulus layer respectively, i.e. in anode side, and barrier film annulus layer front layer to be exceeded cathode ring layer, and at cathode-side, barrier film annulus layer front layer to be exceeded anode annulus layer;
D () is printed after, in argon shield quartz tube furnace, anneal under 600 DEG C of hot conditionss 2h, makes electrode, barrier film solidify;
E () electrode, barrier film make after, with cut thin-walled polymethyl methacrylate, put into the battery structure prepared, major part space is sealed with PolyDiMethylSiloxane gel, solidify at a temperature of 150 DEG C, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra PolyDiMethylSiloxane gel.
The 3D Method of printing of lithium battery the most according to claim 1, it is characterised in that: described cathode and anode and producing of barrier film slurry are carried out as follows,
(1) take the highly enriched lithium titanate 4-5g that weight ratio is 57% to be dispersed in the deionized water of 140-160mL and the sodium lauryl sulphate of 9-14g and form the first mixed solution;Separately take the LiFePO4 2-4g that weight ratio is 60% to be scattered in the sodium lauryl sulphate of 110-130 ml deionized water and 9-14g and form the second mixed solution;
(2) the first mixed solution obtained and the second mixed solution left at room temperature 40-50 hour respectively, and be centrifuged 2-3 hour under 4000rpm, collect the granule of a diameter of 170-190nm, the solid obtained is dispersed back into glycerol respectively, carboxymethyl starch sodium, in the 3rd mixed solution that Kollidone 90F and sodium carboxymethyl cellulose are formed, and ultrasonic 2-3h, thus respectively obtain the first slurry and the second slurry, wherein glycerol in the 3rd mixed solution, carboxymethyl starch sodium, Kollidone 90F and each Composition Weight Parts of sodium carboxymethyl cellulose are respectively 10-13 part, 4-8 part, 3-5 part and 3-5 part;
(3) the first slurry obtained i.e. lithium titanate slurry, as Anode of lithium cell slurry;Obtained the second slurry i.e. LiFePO4 slurry, as lithium cell cathode slurry;
(4) subsequently, the first slurry and the second slurry the most at room temperature solvent flashing, until solid masses ratio is during for 55-65% in slurry, finally prepare the cathode and anode slurry printed in order to 3D;
(5) polyimide diaphragm blank preparation technics: under the conditions of-3 DEG C, it is the 4 of 1mol/L by pyromellitic acid anhydride and 5-10mL concentration that 5-10mL concentration is 1mol/L, 4'-diaminodiphenyl ether and with 4, the N of 4'-diaminodiphenyl ether equimolar amounts, N-dimethyl acetylamide carries out polycondensation reaction and generates polyamic acid, thus obtains the original polyamic acid solution of the solids content with 15%;At a temperature of 60 DEG C after dried overnight, it is heated to 100-300 DEG C with 3 DEG C/min, it is achieved hot imidization;Then it is incorporated in 110-130mL deionized water and 30-50mL ethylene glycol mixed solution, after at room temperature standing 24h, take out precipitate, again precipitate is further distributed in the mixed solution that the glycerol of 10-13 part, the hydroxypropyl cellulose of 3-5 part and 3-4 part hydroxyethyl cellulose are formed, prepares barrier film slurry.
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