CN104409774A - 3D printing method of lithium battery - Google Patents
3D printing method of lithium battery Download PDFInfo
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- CN104409774A CN104409774A CN201410237589.7A CN201410237589A CN104409774A CN 104409774 A CN104409774 A CN 104409774A CN 201410237589 A CN201410237589 A CN 201410237589A CN 104409774 A CN104409774 A CN 104409774A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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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
Technical field
The present invention relates to a kind of 3D Method of printing 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 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.Based on other structure lithium ion battery prepared by 3D printing technique, still there is the problem of 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 overlapping successively based on 3D printing technique negative electrode, barrier film and anode.The inventive method mainly comprises: first prepare the positive and negative electrode slurry needed for 3D printing and barrier film slurry thereof; Again each slurry printed respectively the positive and negative electrode of lithium battery and be positioned at above-mentioned electrode diaphragm layer between the two, subsequently, through Overheating Treatment, packaging technology, finally obtaining the annular lithium ion battery that negative electrode, barrier film and anode are overlapping successively.The present invention is based on 3D printing technique and prepare negative electrode, barrier film and anode annular lithium ion battery overlapping successively, there is preparation method's novelty, technique is simple, controllable precise, and prepared material has specific cathode, barrier film and anode overlapping distributed architecture, large specific area successively; Each negative electrode, barrier film and anode annulus material itself a composition miniature lithium ion battery, 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 following technical scheme:
A 3D Method of printing for lithium battery, to utilize 3D printing technique to print with lithium titanate be anode material, be barrier film with polyimides, take LiFePO4 as the lamination circular ring electrode structure of cathode material.Subsequently; to obtain after heat treatment with lithium titanate under argon shield be anode material, be barrier film with polyimides, take LiFePO4 as the lamination annular composite material of cathode material; then, transfer in glove box and encapsulate, finally obtain lamination circular ring electrode lithium ion battery.
Preparation method of the present invention comprises the steps:
A 3D Method of printing for lithium battery, its preparation method comprises the following steps:
(1) the cathode and anode slurry needed for 3D printing is prepared;
(2) barrier film slurry is prepared;
(3) by obtained slurry, with 30 μm of 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, adapt in tube furnace at argon gas gas shielded, anneal under 600 degree of hot conditionss 2h, and electrode, barrier film are solidified;
(5) after electrode, barrier film make, with laser cutting thin-walled methyl methacrylate, put into the battery structure prepared, most of space is sealed with PolyDiMethylSiloxane gel, solidify at 150 degree of temperature, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra dimethyl silicone polymer.
Described positive and negative electrode and barrier film slurry produce as follows:
(1) get weight ratio be 57% highly enriched lithium titanate 4-5g be dispersed in the deionized water of 140-160ml and the lauryl sodium sulfate of 9-14g and form the first mixed solution; The LiFePO4 2-4g separately getting 60% is scattered in the lauryl sodium sulfate of 110-130 ml deionized water and 9-14g and forms the second mixed solution;
(2) the first mixed solution obtained and the second mixed solution flood 40-50 hour under room temperature respectively, and under 4000rpm centrifugal 2-3 hour, it is 170-190nm that collecting granules controls at diameter, the solid obtained is distributed to glycerine respectively again, sodium carboxymethyl starch, in the 3rd mixed solution that PVP homopolymers and sodium carboxymethylcellulose are formed, and ultrasonic 2-3h, thus obtain the first slurry and the second slurry respectively, wherein glycerine in the 3rd mixed solution, sodium carboxymethyl starch, in PVP homopolymers and sodium carboxymethylcellulose, each Ingredient percent is respectively 10-13%, 4-8%, 3-5% and 3-5%,
(3) the first slurry obtained, namely the composition of lithium titanate slurry is 20-29% glycerine, 20-30% lauryl sodium sulfate, 7-11% sodium carboxymethyl starch, 3-5% PVP homopolymers, the sodium carboxymethylcellulose of 2-3% and deionized water, as cathode of lithium battery slurry; Obtain the second slurry and LiFePO4 slurry composition be 20-30% glycerine, 20-30% lauryl sodium sulfate, 7-9% sodium carboxymethyl starch, 2-3% sodium carboxymethylcellulose, 3-5% PVP homopolymers and deionized water, as lithium battery anode slurry;
(4) subsequently, the first slurry and the second slurry respectively at room temperature solvent flashing until in slurry solid masses be advisable than for during 55-65%, finally prepare in order to 3D lithium battery print anode and cathode slurry;
(5) 5-10ml concentration is 1mol.L by polyimide diaphragm material preparation process: under-3 DEG C of conditions
-1pyromellitic acid dianhydride and 5-10ml concentration be 1mol.L
-14,4'-diaminodiphenyl ethers and etc. the DMA of molal weight carry out polycondensation reaction and generate polyamic acid, thus obtain the original polyamic acid solution with the solids content of 15%; At 60 DEG C of temperature after dried overnight, it is heated to 100-300 DEG C with 3 DEG C/min, realizes hot imidization; Then be incorporated in 110-130ml deionized water and 30-50ml ethylene glycol mixed solution, after at room temperature flooding 24h, take out sediment, again sediment is distributed to further in the mixed solution that the glycerine of 10-13%, the hydroxypropyl cellulose of 3-5% and 3-4% water hydroxyethylcellulose form, finally obtained polyimides paste composition is the glycerine of 20-30%, the ethylene glycol of 20-30%, the hydroxypropyl cellulose of 7-10%, the hydroxyethylcellulose of 2-4% and deionized water, prepare its barrier film slurry.
Described septation and positive and negative electrode are respectively some layers of circular array and form, and described barrier film is between positive and negative electrode layer, and its concrete printing step unification 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) the lower half circle part of the adjacent top of printing step (4) molded annular;
(6) second half circular portion of the molded lower half circle part of printing step (5);
(7) from molded annulus, print its adjacent top lower half circle and second half circular portion is continued, until another semicircle of completing steps (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 cathode material annulus will cover battery metal negative electrode, and all anode material annulus layers require to cover battery metal anode; Simultaneously in order to effectively isolate each anode and cathode electrode layer, membrane layer annulus layer will cover completely respectively and exceed corresponding anode and cathode electrode, and namely on metal anode limit, barrier film annulus will exceed front layer cathode ring layer, and on metallic cathode limit, barrier film annulus will exceed front layer anode annulus layer.
The present invention is based on 3D printing technique and prepare negative electrode, barrier film and anode annular lithium ion battery overlapping successively, preparation method is novel, technique is simple, controllable precise, and prepared material has specific cathode, barrier film and anode overlapping distributed architecture, large specific area successively; Each negative electrode, barrier film and anode annulus material itself a composition miniature lithium ion battery, 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.
Embodiment
The present invention aims to provide a kind of 3D Method of printing of lithium battery, existing by reference to the accompanying drawings and concrete execution mode illustrate
Embodiment 1
1) get weight ratio be 57% highly enriched lithium titanate 4g be dispersed in the deionized water of 140ml and the lauryl sodium sulfate of 9g and form the first mixed solution; Separately get weight ratio be 60% LiFePO4 2g be scattered in the lauryl sodium sulfate of 110ml deionized water and 9g and form the second mixed solution;
2) the first mixed solution and the second mixed solution are at room temperature flooded 40 hours respectively, under 4000rpm centrifugal 2 hours, the Grain size controlling gathered is 170nm at diameter, the particle collected respectively by be again distributed to weight ratio be 10% glycerine, weight ratio be 4% sodium carboxymethyl starch, weight ratio be 3% PVP homopolymers (PVP), weight ratio is in 3% sodium carboxymethylcellulose, and it is ultrasonic to carry out 2h, thus generation homogenate, be denoted as the first slurry and the second slurry respectively;
3) the lithium titanate homogenate prepared is the glycerine of 20%, the lauryl sodium sulfate of 20%, the sodium carboxymethyl starch of 7%, 3% PVP homopolymers (PVP), the sodium carboxymethylcellulose of 2% and deionized water, as cathode of lithium battery slurry; The LiFePO4 homogenate prepared is 20% glycerine, the lauryl sodium sulfate of 20%, 7% sodium carboxymethyl starch, 2% sodium carboxymethylcellulose, and 3% PVP homopolymers (PVP) and deionized water, as lithium battery anode slurry;
4), when at room temperature solvent flashing to homogenate solid masses ratio is 55% respectively by cathode of lithium battery slurry and anode sizing agent, finally the anode and cathode slurry printed in order to 3D lithium battery is obtained;
5) 5ml concentration is 1mol.L by polyimide diaphragm material preparation process: under-3 DEG C of conditions
-1pyromellitic acid dianhydride (PMDA) and 5ml concentration be 1mol.L
-14,4'-diaminodiphenyl ethers (ODA) and etc. the DMA (DMAC) of molal weight carry out polycondensation reaction and generate polyamic acid (PAA), thus obtain the original PAA solution with the solids content of 15%.At 60 DEG C of temperature after dried overnight, it is heated to 100 DEG C with 3 DEG C/min, realizes hot imidization.Then be incorporated in 110ml deionized water and 30ml ethylene glycol mixed solution, after at room temperature flooding 24h, take out sediment, again sediment is distributed to further in the mixed solution that the glycerine of 10%, the hydroxypropyl cellulose of 3% and 3% water hydroxyethylcellulose form, finally obtained polyimides paste composition is the glycerine of 20%, the ethylene glycol of 20%, the hydroxypropyl cellulose of 7%, the hydroxyethylcellulose of 2% and deionized water, prepare its barrier film slurry.
6) slurry obtained before, uses 30um shower nozzle, at 600psi(Pounds per square inch, pressure unit) under print with 250um/s.Its concrete printing step unification 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) the lower half circle part of the adjacent top of printing step (4) molded annular;
(6) second half circular portion of the molded lower half circle part of printing step (5);
(7) from molded annulus, print its adjacent top lower half circle and second half circular portion is continued, until another semicircle of completing steps (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.The roughly figure that one deck prints is as Fig. 1-4.Three-dimensionally shaped figure in reality as shown in Figure 5.
(9) as shown in Figure 6, in battery electrode lead portion, all cathode material annulus will cover battery metal negative electrode, and all anode material annulus layers require to cover battery metal anode.Simultaneously in order to effectively isolate each anode and cathode electrode layer, membrane layer annulus layer will cover completely respectively and exceed corresponding anode and cathode electrode, and namely on metal anode limit, barrier film annulus will exceed front layer cathode ring layer, and on metallic cathode limit, barrier film annulus will exceed front layer anode annulus layer.
7) after printed, with under argon gas gas shielded in test tube stove, with 600 degree of high annealing 2h.Such electrode, barrier film are prepared complete.
8) after electrode, barrier film make.With laser cutting thin-walled methyl methacrylate (PMMA), put into the battery structure prepared, most of space is sealed with dimethyl silicone polymer (PDMS) gel, solidify at 150 degree of temperature, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra PDMS.
Embodiment 2
1) get weight ratio be 57% highly enriched lithium titanate 4.5g be dispersed in the deionized water of 150ml and the lauryl sodium sulfate of 11g and form the first mixed solution; Separately get weight ratio be 60% LiFePO4 3g be scattered in the lauryl sodium sulfate of 120ml deionized water and 11g and form the second mixed solution;
2) the first mixed solution and the second mixed solution are at room temperature flooded 45 hours respectively, under 4000rpm centrifugal 2.5 hours, the Grain size controlling gathered is 180nm at diameter, the particle collected respectively by be again distributed to weight ratio be 12% glycerine, weight ratio be 6% sodium carboxymethyl starch, weight ratio be 4% PVP homopolymers (PVP), weight ratio is in 4% sodium carboxymethylcellulose, and it is ultrasonic to carry out 2.5h, thus generation homogenate, be denoted as the first slurry and the second slurry respectively;
3) the lithium titanate homogenate prepared is the glycerine of 25%, the lauryl sodium sulfate of 25%, the sodium carboxymethyl starch of 9%, 4% PVP homopolymers (PVP), the sodium carboxymethylcellulose of 2.5% and deionized water, as cathode of lithium battery slurry; The LiFePO4 homogenate prepared is 25% glycerine, the lauryl sodium sulfate of 25%, 8% sodium carboxymethyl starch, 2.5% sodium carboxymethylcellulose, and 4% PVP homopolymers (PVP) and deionized water, as lithium battery anode slurry;
4), when at room temperature solvent flashing to homogenate solid masses ratio is 60% respectively by cathode of lithium battery slurry and anode sizing agent, finally the anode and cathode slurry printed in order to 3D lithium battery is obtained;
5) 7ml concentration is 1mol.L by polyimide diaphragm material preparation process: under-3 DEG C of conditions
-1pyromellitic acid dianhydride (PMDA) and 7ml concentration be 1mol.L
-14,4'-diaminodiphenyl ethers (ODA) and etc. the DMA (DMAC) of molal weight carry out polycondensation reaction and generate polyamic acid (PAA), thus obtain the original PAA solution with the solids content of 15%.At 60 DEG C of temperature after dried overnight, it is heated to 200 DEG C with 3 DEG C/min, realizes hot imidization.Then be incorporated in 120ml deionized water and 40ml ethylene glycol mixed solution, after at room temperature flooding 24h, take out sediment, again sediment is distributed to further in the mixed solution that the glycerine of 12%, the hydroxypropyl cellulose of 4% and 3.5% water hydroxyethylcellulose form, finally obtained polyimides paste composition is the glycerine of 25%, the ethylene glycol of 25%, the hydroxypropyl cellulose of 8%, the hydroxyethylcellulose of 3% and deionized water, prepare its barrier film slurry.
6) slurry obtained before, uses 30um shower nozzle, at 600psi(Pounds per square inch, pressure unit) under print with 250um/s.Its concrete printing step unification 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) the lower half circle part of the adjacent top of printing step (4) molded annular;
(6) second half circular portion of the molded lower half circle part of printing step (5);
(7) from molded annulus, print its adjacent top lower half circle and second half circular portion is continued, until another semicircle of completing steps (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.The roughly figure that one deck prints is as Fig. 1-4.Three-dimensionally shaped figure in reality as shown in Figure 5.
(9) as shown in Figure 6, in battery electrode lead portion, all cathode material annulus will cover battery metal negative electrode, and all anode material annulus layers require to cover battery metal anode.Simultaneously in order to effectively isolate each anode and cathode electrode layer, membrane layer annulus layer will cover completely respectively and exceed corresponding anode and cathode electrode, and namely on metal anode limit, barrier film annulus will exceed front layer cathode ring layer, and on metallic cathode limit, barrier film annulus will exceed front layer anode annulus layer.
7) after printed, with under argon gas gas shielded in test tube stove, with 600 degree of high annealing 2h.Such electrode, barrier film are prepared complete.
8) after electrode, barrier film make.With laser cutting thin-walled methyl methacrylate (PMMA), put into the battery structure prepared, most of space is sealed with dimethyl silicone polymer (PDMS) gel, solidify at 150 degree of temperature, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra PDMS.
Embodiment 3
1) get weight ratio be 57% highly enriched lithium titanate 5g be dispersed in the deionized water of 160ml and the lauryl sodium sulfate of 14g and form the first mixed solution; Separately get weight ratio be 60% LiFePO4 4g be scattered in the lauryl sodium sulfate of 130ml deionized water and 14g and form the second mixed solution;
2) the first mixed solution and the second mixed solution are at room temperature flooded 50 hours respectively, under 4000rpm centrifugal 3 hours, the Grain size controlling gathered is 190nm at diameter, the particle collected respectively by be again distributed to weight ratio be 13% glycerine, weight ratio be 8% sodium carboxymethyl starch, weight ratio be 5% PVP homopolymers (PVP), weight ratio is in 5% sodium carboxymethylcellulose, and it is ultrasonic to carry out 3h, thus generation homogenate, be denoted as the first slurry and the second slurry respectively;
3) the lithium titanate homogenate prepared is the glycerine of 29%, the lauryl sodium sulfate of 30%, the sodium carboxymethyl starch of 11%, 5% PVP homopolymers (PVP), the sodium carboxymethylcellulose of 3% and deionized water, as cathode of lithium battery slurry; The LiFePO4 homogenate prepared is 30% glycerine, the lauryl sodium sulfate of 30%, 9% sodium carboxymethyl starch, 3% sodium carboxymethylcellulose, and 5% PVP homopolymers (PVP) and deionized water, as lithium battery anode slurry;
4), when at room temperature solvent flashing to homogenate solid masses ratio is 65% respectively by cathode of lithium battery slurry and anode sizing agent, finally the anode and cathode slurry printed in order to 3D lithium battery is obtained;
5) 10ml concentration is 1mol.L by polyimide diaphragm material preparation process: under-3 DEG C of conditions
-1pyromellitic acid dianhydride (PMDA) and 10ml concentration be 1mol.L
-14,4'-diaminodiphenyl ethers (ODA) and etc. the DMA (DMAC) of molal weight carry out polycondensation reaction and generate polyamic acid (PAA), thus obtain the original PAA solution with the solids content of 15%.At 60 DEG C of temperature after dried overnight, it is heated to 300 DEG C with 3 DEG C/min, realizes hot imidization.Then be incorporated in 130ml deionized water and 50ml ethylene glycol mixed solution, after at room temperature flooding 24h, take out sediment, again sediment is distributed to further in the mixed solution that the glycerine of 13%, the hydroxypropyl cellulose of 5% and 4% water hydroxyethylcellulose form, finally obtained polyimides paste composition is the glycerine of 30%, the ethylene glycol of 30%, the hydroxypropyl cellulose of 10%, the hydroxyethylcellulose of 4% and deionized water, prepare its barrier film slurry.
6) slurry obtained before, uses 30um shower nozzle, at 600psi(Pounds per square inch, pressure unit) under print with 250um/s.Its concrete printing step unification 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) the lower half circle part of the adjacent top of printing step (4) molded annular;
(6) second half circular portion of the molded lower half circle part of printing step (5);
(7) from molded annulus, print its adjacent top lower half circle and second half circular portion is continued, until another semicircle of completing steps (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.The roughly figure that one deck prints is as Fig. 1-4.Three-dimensionally shaped figure in reality as shown in Figure 5.
(9) as shown in Figure 6, in battery electrode lead portion, all cathode material annulus will cover battery metal negative electrode, and all anode material annulus layers require to cover battery metal anode.Simultaneously in order to effectively isolate each anode and cathode electrode layer, membrane layer annulus layer will cover completely respectively and exceed corresponding anode and cathode electrode, and namely on metal anode limit, barrier film annulus will exceed front layer cathode ring layer, and on metallic cathode limit, barrier film annulus will exceed front layer anode annulus layer.
7) after printed, with under argon gas gas shielded in test tube stove, with 600 degree of high annealing 2h.Such electrode, barrier film are prepared complete.
8) after electrode, barrier film make.With laser cutting thin-walled methyl methacrylate (PMMA), put into the battery structure prepared, most of space is sealed with dimethyl silicone polymer (PDMS) gel, solidify at 150 degree of temperature, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra PDMS.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (3)
1. a 3D Method of printing for lithium battery, is characterized in that: be prepared as follows,
(1) the cathode and anode slurry needed for 3D printing is prepared;
(2) barrier film slurry is prepared;
(3) by obtained slurry, with 30 μm of 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, adapt in tube furnace at argon gas gas shielded, anneal under 600 degree of hot conditionss 2h, and electrode, barrier film are solidified;
(5) after electrode, barrier film make, with laser cutting thin-walled methyl methacrylate, put into the battery structure prepared, most of space is sealed with PolyDiMethylSiloxane gel, solidify at 150 degree of temperature, before solidification, machine automatization adds electrolyte from space, and seals remaining space with extra dimethyl silicone polymer.
2. the 3D Method of printing of a kind of lithium battery according to right 1, is characterized in that: described positive and negative electrode and producing of barrier film slurry are carried out as follows,
(1) get weight ratio be 57% highly enriched lithium titanate 4-5g be dispersed in the deionized water of 140-160ml and the lauryl sodium sulfate of 9-14g and form the first mixed solution; The LiFePO4 2-4g separately getting 60% is scattered in the lauryl sodium sulfate of 110-130 ml deionized water and 9-14g and forms the second mixed solution;
(2) the first mixed solution obtained and the second mixed solution flood 40-50 hour under room temperature respectively, and under 4000rpm centrifugal 2-3 hour, it is 170-190nm that collecting granules controls at diameter, the solid obtained is distributed to glycerine respectively again, sodium carboxymethyl starch, in the 3rd mixed solution that PVP homopolymers and sodium carboxymethylcellulose are formed, and ultrasonic 2-3h, thus obtain the first slurry and the second slurry respectively, wherein glycerine in the 3rd mixed solution, sodium carboxymethyl starch, in PVP homopolymers and sodium carboxymethylcellulose, each Ingredient percent is respectively 10-13%, 4-8%, 3-5% and 3-5%,
(3) the first slurry obtained, namely the composition of lithium titanate slurry is 20-29% glycerine, 20-30% lauryl sodium sulfate, 7-11% sodium carboxymethyl starch, 3-5% PVP homopolymers, the sodium carboxymethylcellulose of 2-3% and deionized water, as cathode of lithium battery slurry; Obtain the second slurry and LiFePO4 slurry composition be 20-30% glycerine, 20-30% lauryl sodium sulfate, 7-9% sodium carboxymethyl starch, 2-3% sodium carboxymethylcellulose, 3-5% PVP homopolymers and deionized water, as lithium battery anode slurry;
(4) subsequently, the first slurry and the second slurry respectively at room temperature solvent flashing until in slurry solid masses be advisable than for during 55-65%, finally prepare in order to 3D lithium battery print anode and cathode slurry;
(5) 5-10ml concentration is 1mol.L by polyimide diaphragm material preparation process: under-3 DEG C of conditions
-1pyromellitic acid dianhydride and 5-10ml concentration be 1mol.L
-14,4'-diaminodiphenyl ethers and etc. the DMA of molal weight carry out polycondensation reaction and generate polyamic acid, thus obtain the original polyamic acid solution with the solids content of 15%; At 60 DEG C of temperature after dried overnight, it is heated to 100-300 DEG C with 3 DEG C/min, realizes hot imidization; Then be incorporated in 110-130ml deionized water and 30-50ml ethylene glycol mixed solution, after at room temperature flooding 24h, take out sediment, again sediment is distributed to further in the mixed solution that the glycerine of 10-13%, the hydroxypropyl cellulose of 3-5% and 3-4% water hydroxyethylcellulose form, finally obtained polyimides paste composition is the glycerine of 20-30%, the ethylene glycol of 20-30%, the hydroxypropyl cellulose of 7-10%, the hydroxyethylcellulose of 2-4% and deionized water, prepare its barrier film slurry.
3. the 3D Method of printing of a kind of lithium battery according to right 1, is characterized in that: step 3) septation and positive and negative electrode are respectively some layers of circular array and form, and described barrier film is between positive and negative electrode layer, and its concrete printing step unification 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) the lower half circle part of the adjacent top of printing step (4) molded annular;
(6) second half circular portion of the molded lower half circle part of printing step (5);
(7) from molded annulus, print its adjacent top lower half circle and second half circular portion is continued, until another semicircle of completing steps (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 cathode material annulus will cover battery metal negative electrode, and all anode material annulus layers require to cover battery metal anode; Simultaneously in order to effectively isolate each anode and cathode electrode layer, membrane layer annulus layer will cover completely respectively and exceed corresponding anode and cathode electrode, and namely on metal anode limit, barrier film annulus will exceed front layer cathode ring layer, and on metallic cathode limit, barrier film annulus will exceed front layer anode annulus layer.
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