CN106099128A - A kind of three-dimensional lithium battery manufacture method - Google Patents
A kind of three-dimensional lithium battery manufacture method Download PDFInfo
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- CN106099128A CN106099128A CN201610523164.1A CN201610523164A CN106099128A CN 106099128 A CN106099128 A CN 106099128A CN 201610523164 A CN201610523164 A CN 201610523164A CN 106099128 A CN106099128 A CN 106099128A
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/005—Devices for making primary cells
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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
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to technical field of lithium ion, disclose a kind of three-dimensional lithium battery manufacture method, electrode slurry, slurry process, slurries filtration, loading printing slurry, substrate pretreatment, the printing of low temperature direct write 3D, electrode lyophilization, electrode sintering, cell package and note electrolyte operation is printed by configuring 3D, above-mentioned technique is characterised by with method: print positive pole and cathode size, the slurry freeze forming at low temperatures of lithium battery at low ambient temperatures with 3D Method of printing.Three-dimensional lithium battery method of manufacturing technology proposed by the invention is suitable for preparing large scale, high-energy, high-power three-dimensional lithium battery.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of three-dimensional lithium battery manufacture method.
Background technology
Lithium battery, owing to its running voltage is high, energy density is high and has higher cycle life, has become as consumption electricity
The important electrochemical energy storage device of one in the fields such as sub-product, electric vehicle and industry energy storage.Current lithium electricity
The structure in pond includes button-shaped, column type, square structure and film lithium cell, and positive pole and the negative pole structure of above battery are two
Dimensional plane shape, even being wound rear both positive and negative polarity to remain parallel, is the most all two dimension lithium battery.This
Planting battery and have problems in that the contradiction of energy density and power density, in order to improve the energy content of battery, then thickness of electrode should be got over
Big the best, but thickness of electrode increase can cause lithium ion mobility rate reduction, so that power drop.Therefore, the setting of battery
Meter must be accepted or rejected between energy density and power density, and energy density promotes then power density and declines.
In order to promote energy density, not reduce power density and become and realize high-energy-density and high power density lithium battery
Crucial.Conventional electrode configurations is become three dimensional structure from parallel plate type, thus manufactures three-dimensional lithium battery and realize above-mentioned target
Effective ways.Occur in that the design proposing some three-dimensional batteries at present, such as interlocked such as column staggered array type, lamellar
Formula, concentric arry formula and random concentric type.In terms of microcosmic, lithium ion migration between positive and negative electrode remains as one-dimensional diffusion,
Macroscopically seeing, electrode structure is complex three-dimensional structure.Therefore, lithium ion diffusion length is short, can be effectively improved power density；Three-dimensional
Structure increases electrode material total amount on the basis of not increasing thickness of electrode, thus is effectively improved the energy content of battery, reaches to carry simultaneously
High battery energy density and the target of power density.
In prior art, the technique of the three-dimensional lithium battery of preparation specifically includes that photoetching process, silicon micromachining technology and various mould
Plate synthetic method such as anodic oxidation aluminium formwork method, colloidal crystal templates method and biological template method (Biotemplate) etc..Although these
Technology has been achieved for important progress, but these method efficiency is low, cost is high, manufacture three-dimensional in scale, low cost
Lithium battery aspect faces huge challenge.
Summary of the invention
The present invention provides a kind of three-dimensional lithium battery manufacture method, solves the technique effect of the three-dimensional lithium battery of preparation in prior art
The technical problem that rate is low, cost is high.
It is an object of the invention to be achieved through the following technical solutions:
A kind of three-dimensional lithium battery manufacture method, including:
Configuration 3D prints electrode slurry；
Described electrode slurry is filtered；
Electrode slurry after filtering is respectively charged into positive electrode printing head and negative material printing head；
Printed substrates makes plus plate current-collecting body and negative current collector；
Three-dimensional lithium battery design configuration that is at low ambient temperatures, indoor at printing shaping, that preset according to computer, is just using
Pole file printing shower nozzle and negative material printing head carry out 3D printing；
At low ambient temperatures, electrode of lithium cell is carried out frozen drying；
Electrode of lithium cell after lyophilization is put into sintering furnace be sintered at 600 DEG C；
Printed electrode of lithium cell cabinet is encapsulated；
Inject the electrolyte in packaged lithium battery, to form three-dimensional lithium battery.
The present invention provides a kind of three-dimensional lithium battery manufacture method, prints electrode slurry by configuring 3D；To described electrode slurry
Material filters；Electrode slurry after filtering is respectively charged into positive electrode printing head and negative material printing head；Beating
Substrates printed upper making plus plate current-collecting body and negative current collector；At low ambient temperatures, indoor at printing shaping, preset according to computer
Three-dimensional lithium battery design configuration, use positive electrode printing head and negative material printing head to carry out 3D printing；At low temperature
Under environment, electrode of lithium cell is carried out frozen drying；Electrode of lithium cell after lyophilization is put into sintering furnace 600
DEG C it is sintered；Printed electrode of lithium cell cabinet is encapsulated；Inject the electrolyte into packaged lithium electricity
Chi Zhong, to form three-dimensional lithium battery.Three-dimensional lithium battery method of manufacturing technology proposed by the invention is suitable for preparing large scale, height
Energy, high-power three-dimensional lithium battery.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to institute in embodiment
The accompanying drawing used is needed to be briefly described, it should be apparent that, the accompanying drawing in describing below is only some enforcements of the present invention
Example, for those of ordinary skill in the art, on the premise of not paying creative work, also can obtain according to these accompanying drawings
Obtain other accompanying drawing.
Fig. 1 is the flow chart of a kind of three-dimensional lithium battery manufacture method of the embodiment of the present invention.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, real with concrete below in conjunction with the accompanying drawings
The present invention is further detailed explanation to execute mode.
As it is shown in figure 1, a kind of three-dimensional lithium battery manufacture method provided for the embodiment of the present invention, including:
Step 101, configuration 3D print electrode slurry；
Wherein, by positive electrode powder body (such as LiCoO2、LiFePO4、LiMn2O4)With negative electrode material powder (such as Li4Ti5O12、
Graphite) (PVAC polyvinylalcohol, carboxymethyl are fine with organic solvent (1,4 dioxane), conductive agent (white carbon black) and thickening agent/binding agent
Dimension element sodium CMC etc.) according to mass fraction according to carrying out mix homogeneously, wherein the mass fraction of electrode active material be 50%～
80%, the mass fraction of organic solvent is 20%～50%, and conductive agent mass fraction is 1%～2%, the mass fraction of binding agent
It is 2%～3%, after mixing, makes active material powder body dispersed.This step print electrode slurry range of viscosities be 10～
100Pa.s.Described powder body is available micron particles or nano-scale particle, and micron particle mean diameter is 1～10 μm, nanoscale
Mean particle size is 50～200nm.Thickening agent is hydroxypropyl cellulose or sodium carboxymethyl cellulose.Organic solvent is 1,4 2
Oxygen six ring.Conductive agent is white carbon black.
Step 102, electrode slurry is filtered；
Wherein, the size of the Fe impurity in this step removal slurry and reunion is relatively big, affect the micro-of print procedure stability
Grain, to optimize size performance, to promote slurry quality, it is ensured that will not block shower nozzle in print procedure.
Step 103, will filter after electrode slurry be respectively charged into positive electrode printing head and negative material printing head；
Step 104, in printed substrates, make plus plate current-collecting body and negative current collector；
Wherein, described printed substrates is glass, pottery or plastics, and glass basic surface collector can use photoetching and electron beam
The techniques such as evaporation make.Available laser direct forming LDS (laser direct structuring) on pottery and plastic-substrates
Technique makes, and is i.e. radiated in the plastic-substrates containing metal complex or ceramic bases surface with laser, the table that laser irradiates
Metallic can be exposed in face, can carry out chemical plating as the matrix of chemical plating and make the printed substrates with collector.
Step 105, at low ambient temperatures, indoor at printing shaping, the three-dimensional lithium battery design drawing preset according to computer
Shape, uses positive electrode printing head and negative material printing head to carry out 3D printing；
Wherein, low temperature is-20 DEG C～-30 DEG C, and described printing shaping room is wrapped up by heat insulation mantle, with surroundings outside
Separate, it is ensured that the temperature in forming room.Forming room is carried out, to it, the temperature control that freezes by a set of refrigeration unit, including compressor, condensation
Device, expansion valve, vaporizer, crossflow fan and cold air inlet and outlet, whole print procedure is carried out on forming bottom plate.
Step 106, at low ambient temperatures, carries out frozen drying to electrode of lithium cell；
Wherein, the electrode of printing shaping is immediately placed in low-temperature freeze-drying machine low temperature environment below vacuum and-50 DEG C
In be dried process so that the distillation of organic solvent in electrode, stay containing organic adhesive, thickening agent and electrode activity material
The dried electrode of material composition.
Step 107, the electrode of lithium cell after lyophilization is put into sintering furnace it is sintered at 600 DEG C；
Wherein, the organic component in electrode is ablated, bonding strength is greatly improved between electrode active material particles, sintering
After electrode can be directly as the positive pole of lithium battery and negative pole.
Step 108, printed electrode of lithium cell cabinet is encapsulated；
Printed lithium battery anode and cathode of lithium battery cabinet are encapsulated, and ensure the battery after encapsulation
There is good sealing.
Step 109, inject the electrolyte in packaged lithium battery, to form three-dimensional lithium battery.
Three-dimensional lithium battery method of manufacturing technology proposed by the invention, compared with conventional technique, it is possible to obtain have below
Benefit effect: (1) is printed by low temperature direct write 3D, and whole print procedure is in the low temperature environment of less than-30 DEG C, the slurry after printing
Can curing molding rapidly, be effectively increased the mechanical strength printing microfilament, print structure will not in material layers banking process
Cave in, such that it is able to manufacture the three-dimensional lithium battery that size is bigger.(2) after the structure printed molding at low temperatures, internal
Organic solvent crystallizes, and then carries out frozen drying, forms hundreds of nanometer after organic solvent volatilization in printing electrode
～the pore structure of tens microns, prepare micro-nano porous electrode, this pore structure is conducive to electrolyte to enter electrode interior,
The specific surface area of the most this electrode is greatly increased, thus can be effectively improved the power density of battery, bigger electrode surface area
Also help reduction current surface density, reduce electrode polarization overpotential, improve battery performance.Therefore, proposed by the invention three
Dimension lithium battery method of manufacturing technology is suitable for preparing large scale, high-energy, high-power three-dimensional lithium battery.
Being described in detail the present invention above, specific case used herein is to the principle of the present invention and embodiment party
Formula is set forth, and the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention；Meanwhile, right
In one of ordinary skill in the art, according to the thought of the present invention, the most all can change
Part, in sum, this specification content should not be construed as limitation of the present invention.
Claims (5)
1. a three-dimensional lithium battery manufacture method, it is characterised in that including:
Configuration 3D prints electrode slurry；
Described electrode slurry is filtered；
Electrode slurry after filtering is respectively charged into positive electrode printing head and negative material printing head；
Printed substrates makes plus plate current-collecting body and negative current collector；
Three-dimensional lithium battery design configuration that is at low ambient temperatures, indoor at printing shaping, that preset according to computer, uses positive pole material
Material printing head and negative material printing head carry out 3D printing；
At low ambient temperatures, electrode of lithium cell is carried out frozen drying；
Electrode of lithium cell after lyophilization is put into sintering furnace be sintered at 600 DEG C；
Printed electrode of lithium cell cabinet is encapsulated；
Inject the electrolyte in packaged lithium battery, to form three-dimensional lithium battery.
Three-dimensional lithium battery manufacture method the most according to claim 1, it is characterised in that described configuration 3D prints electrode slurry
Step, including:
Positive electrode powder body by 50%～80% and negative electrode material powder with 20%～50% organic solvent, 1%～2%
Conductive agent and the thickening agent of 2%～3% or binding agent carry out mix homogeneously, so that active material powder body is dispersed, wherein, just
Pole material includes that LiCoO2, LiFePO4, LiMn2O4, negative material include Li4Ti5O12, graphite, and organic solvent is Isosorbide-5-Nitrae dioxy
Six rings, conductive agent is white carbon black, and thickening agent is PVAC polyvinylalcohol or sodium carboxymethyl cellulose CMC.
Three-dimensional lithium battery manufacture method the most according to claim 1, it is characterised in that described just make in printed substrates
Pole collector and the step of negative current collector, including:
When printed substrates is substrate of glass, photoetching and electron beam evaporation is used to make plus plate current-collecting body and negative current collector；
When printed substrates is pottery or plastics, laser direct forming is used to make plus plate current-collecting body and negative current collector.
Three-dimensional lithium battery manufacture method the most according to claim 1, it is characterised in that described at low ambient temperatures, to lithium
Battery electrode carries out the step of frozen drying, including:
The electrode of lithium cell of printing shaping is immediately placed in low-temperature freeze-drying machine low temperature environment below vacuum and-50 DEG C
Row dried so that the organic solvent distillation in electrode, stays containing organic adhesive, thickening agent and electrode active material group
The dried electrode become.
Three-dimensional lithium battery manufacture method the most according to claim 1, it is characterised in that described described electrode slurry is carried out
The step filtered, including:
The size filtering Fe impurity and the reunion removed in slurry is relatively big, affect the microgranule of print procedure stability.
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| CN201610523164.1A CN106099128A (en) | 2016-07-05 | 2016-07-05 | A kind of three-dimensional lithium battery manufacture method |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450334A (en) * | 2016-11-24 | 2017-02-22 | 青岛尤尼科技有限公司 | Lithium battery cathode plate with graphene conductive framework, lithium battery and preparation method |
| CN107170953A (en) * | 2017-05-12 | 2017-09-15 | 西安工程大学 | A kind of warm therapy powdery electrode printed material and its preparation method for printing electrode |
| CN108288696A (en) * | 2018-01-11 | 2018-07-17 | 江苏合志新能源材料技术有限公司 | Electrode material that specific surface area reduces and preparation method thereof and lithium ion battery |
| CN109309193A (en) * | 2018-09-13 | 2019-02-05 | 深圳光韵达机电设备有限公司 | The lithium ion cell electrode structure and its processing method of high-specific surface area and application |
| CN109774126A (en) * | 2018-12-29 | 2019-05-21 | 深圳大学 | Device, method and the three-dimensional lithium ion battery of 3D printing three-dimensional lithium ion battery |
| CN110112370A (en) * | 2019-06-19 | 2019-08-09 | 哈尔滨工业大学 | A kind of self-supporting silicon-graphene combination electrode preparation method based on 3D printing |
| CN110350148A (en) * | 2019-06-10 | 2019-10-18 | 西安工程大学 | Lithium ion battery Porous Silicon Electrode based on 3D printing technique and preparation method thereof |
| CN110518218A (en) * | 2019-09-04 | 2019-11-29 | 衢州学院 | New energy electrode material of lithium battery and production method based on 3D printing |
| WO2020147153A1 (en) * | 2019-01-15 | 2020-07-23 | 梅承寨 | Lithium battery production process |
| CN112125347A (en) * | 2020-08-27 | 2020-12-25 | 中冶长天国际工程有限责任公司 | Low-energy-consumption rapid lithium cobaltate preparation method and system |
| CN112467083A (en) * | 2020-11-20 | 2021-03-09 | 南京理工大学 | Method for 3D printing of three-dimensional cathode |
| CN114420895A (en) * | 2021-12-31 | 2022-04-29 | 荆门市格林美新材料有限公司 | Method for preparing ternary positive electrode plate based on 3D printing technology |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450334A (en) * | 2016-11-24 | 2017-02-22 | 青岛尤尼科技有限公司 | Lithium battery cathode plate with graphene conductive framework, lithium battery and preparation method |
| CN107170953A (en) * | 2017-05-12 | 2017-09-15 | 西安工程大学 | A kind of warm therapy powdery electrode printed material and its preparation method for printing electrode |
| CN108288696A (en) * | 2018-01-11 | 2018-07-17 | 江苏合志新能源材料技术有限公司 | Electrode material that specific surface area reduces and preparation method thereof and lithium ion battery |
| CN109309193A (en) * | 2018-09-13 | 2019-02-05 | 深圳光韵达机电设备有限公司 | The lithium ion cell electrode structure and its processing method of high-specific surface area and application |
| CN109774126A (en) * | 2018-12-29 | 2019-05-21 | 深圳大学 | Device, method and the three-dimensional lithium ion battery of 3D printing three-dimensional lithium ion battery |
| WO2020147153A1 (en) * | 2019-01-15 | 2020-07-23 | 梅承寨 | Lithium battery production process |
| CN110350148A (en) * | 2019-06-10 | 2019-10-18 | 西安工程大学 | Lithium ion battery Porous Silicon Electrode based on 3D printing technique and preparation method thereof |
| CN110350148B (en) * | 2019-06-10 | 2022-04-26 | 西安工程大学 | Lithium ion battery porous silicon electrode based on 3D printing technology and preparation method thereof |
| CN110112370A (en) * | 2019-06-19 | 2019-08-09 | 哈尔滨工业大学 | A kind of self-supporting silicon-graphene combination electrode preparation method based on 3D printing |
| CN110518218A (en) * | 2019-09-04 | 2019-11-29 | 衢州学院 | New energy electrode material of lithium battery and production method based on 3D printing |
| CN112125347A (en) * | 2020-08-27 | 2020-12-25 | 中冶长天国际工程有限责任公司 | Low-energy-consumption rapid lithium cobaltate preparation method and system |
| CN112125347B (en) * | 2020-08-27 | 2022-05-03 | 中冶长天国际工程有限责任公司 | Low-energy-consumption rapid preparation method of lithium cobaltate |
| CN112467083A (en) * | 2020-11-20 | 2021-03-09 | 南京理工大学 | Method for 3D printing of three-dimensional cathode |
| CN114420895A (en) * | 2021-12-31 | 2022-04-29 | 荆门市格林美新材料有限公司 | Method for preparing ternary positive electrode plate based on 3D printing technology |
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