CN107170956A - All-solid-state flexible one electrochemical cell and its preparation method using 3D printing - Google Patents

All-solid-state flexible one electrochemical cell and its preparation method using 3D printing Download PDF

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CN107170956A
CN107170956A CN201710430008.5A CN201710430008A CN107170956A CN 107170956 A CN107170956 A CN 107170956A CN 201710430008 A CN201710430008 A CN 201710430008A CN 107170956 A CN107170956 A CN 107170956A
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negative
positive
ink
pole
positive pole
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CN107170956B (en
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陈立宝
周林
韦伟峰
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Central South University
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • 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)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to the integral electrochemical cell of all-solid-state flexible and its preparation method using 3D printing.The integrated battery of the all-solid-state flexible includes soft shell, flexible positive pole, flexible negative pole, flexible solid electrolyte.Its preparation method is first to etch the groove of required shape by design size on a flexible substrate, then in bottom surface deposited metal aluminium and metallic copper respectively as plus plate current-collecting body and negative current collector；The positive electrode ink configured and negative electrode ink are installed in syringe respectively, is printed upon in layers with 3D printer successively on plus plate current-collecting body with negative current collector, forms multilayer positive pole and multilayer negative pole；Electrolyte ink is printed between multilayer positive pole and multilayer negative pole, forms electrolyte.The present invention combines 3D printing technique with the manufacture of all-solid-state flexible battery, has obtained with the high product of high security, wearable property, energy density height, good cycle, high rate performance, while it prepares convenient controllability height, is easy to large-scale application.

Description

All-solid-state flexible one electrochemical cell and its preparation method using 3D printing
Technical field
The present invention relates to the integral electrochemical cell of all-solid-state flexible and its preparation method using 3D printing；Belong to energy device, All-solid-state battery, flexible battery design and preparing technical field.
Background technology
Compared with using the conventional batteries of liquid electrolyte, all-solid-state battery does not have to concern the danger of electrolyte leakage, peace Full property is more preferable；The decomposition voltage of liquid electrolyte can limit the potential window of battery, reduce the energy density of battery, all solid state electricity Pond can use broader potential window, improve energy density.
With the development of wearable electronic, corresponding is the demand to flexible energy storage device, and flexible battery is It is wherein the most typical to represent.Flexible battery can bear certain deformation stretching and self performance does not decline.What is existed now is soft Property battery manufacture method can only obtain the flexible electrode or battery of plane stratiform, not only limit the shape of battery, and resistance Hinder the raising of energy density, power density, and then limit the development and application of its own.
3D printing technique automatically, quickly, directly and relatively accurately by the three dimensional design in computer can be converted into reality Thing model, saves number of assembling steps, simplifies production, saves the time, improves efficiency, reduces cost.It can accurately and quickly be manufactured Go out miniature complex devices.Traditional battery manufacturing process can not produce the battery of microminiature, but based on 3D printing rapid shaping Technology, can manufacture small battery.This will greatly expand the application field of battery, such as microrobot, microsensor.
The content of the invention
The present invention devises a kind of integral electrochemical cell of all-solid-state flexible first, while further developed all-solid-state flexible one The preparation method of electrochemical cell, is combined by 3D printing technique with the manufacture of all-solid-state flexible battery, by configuring with certain soft The active material ink of property, and using 3D direct writes forming machine efficiently produce a kind of energy density height, it is good cycle, forthright again Can the high and reliable all-solid-state flexible all-in-one micro battery of security.Security, the flexible electrical of this battery collection all-solid-state battery Wearable property, the characteristic of the convenient automation of 3D printing technique in pond are integrated, and are had a wide range of applications.
The integral electrochemical cell of all-solid-state flexible of the present invention, including soft shell, flexible positive pole, flexible negative pole, flexible solid electricity Xie Zhi；
The flexible positive pole includes plus plate current-collecting body and flexible solid substance A；The flexible solid substance A is mixed by liquid Thing B is obtained after drying process, and the initial elastic modulus of the liquefied mixture B is more than 10000Pa and modulus of elasticity is higher than consumption Dissipate modulus；The critical shearing stress of the liquefied mixture B is between 100~10000Pa；The liquefied mixture B is by positive pole Active material, positive pole toughener, positive pole thickener, positive pole dispersant, positive pole solvent composition, the granularity of the positive active material Less than or equal to 10 microns；
The flexible negative pole includes negative current collector and flexible solid substance C；The flexible solid substance C is mixed by liquid Thing D is obtained after drying process, and the initial elastic modulus of the liquefied mixture D is more than 10000Pa and modulus of elasticity is higher than consumption Dissipate modulus；The critical shearing stress of the liquefied mixture D is between 100~10000Pa；The liquefied mixture D is by negative pole Active material, negative pole toughener, negative pole thickener, negative pole dispersant, negative pole solvent composition, the granularity of the negative electrode active material Less than or equal to 10 microns；
Flexible solid electrolyte is obtained by liquefied mixture E after drying process, the initial elasticity of the liquefied mixture E Modulus is more than 100Pa, and modulus of elasticity is higher than dissipation modulus, when shear rate is γ=1S-1When, viscosities il=101~ 102Pa·S。
Preferably, the positive pole toughener is CNT.
Preferably, the positive pole thickener is selected from carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose At least one of.
Preferably, the positive pole dispersant is selected from cetyl trimethylammonium bromide (CTAB), dodecyl sulphur At least one of sour sodium (SDS), neopelex (SDBS).
As further preferred scheme, in liquefied mixture B, the mass ratio of positive active material and deionized water is 1: 3~4.5, it is preferably 1:3；The mass ratio of positive active material and positive pole toughener is 20:1~2:1st, still more preferably positive pole The mass ratio of active material and positive pole toughener is 20:1~5:1, the mass ratio of active material and positive pole thickener is 25:1~ 40:1.When positive pole toughener is CNT, its content is higher, and material flexibility is higher, but comparatively battery specific capacity meeting Decline.Dispersant is used to disperse positive pole toughener, and the mass ratio of itself and positive pole toughener is 0.15~0.25:1；
Preferably, the positive pole solvent is made up of water and/or ethanol.Further preferably, the positive pole solvent by Water and/or ethanol by volume 3:2~3:1 composition.As further preferred scheme, the positive pole solvent is pressed by water and ethanol Volume ratio 3:2.
Preferably, the negative pole toughener is CNT.
Preferably, the negative pole thickener is selected from carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose At least one of.
Preferably, the negative pole dispersant is selected from cetyl trimethylammonium bromide (CTAB), dodecyl sulphur At least one of sour sodium (SDS), neopelex (SDBS).
Preferably, the negative pole solvent is made up of water and/or ethanol.Further preferably, the negative pole solvent by Water and ethanol by volume 3:2-1, preferably 3:2 compositions.
As further preferred scheme, in liquefied mixture D, the mass ratio of negative electrode active material and deionized water is 1: 3~4.5, it is preferably 1:3；The mass ratio of negative electrode active material and negative pole toughener is 20:1~2:1st, still more preferably negative pole The mass ratio of active material and negative pole toughener is 20:1~5:1, the mass ratio of negative electrode active material and negative pole thickener is 25: 1~40:1.When positive pole toughener is CNT, its content is higher, and material flexibility is higher, but comparatively battery specific capacity It can decline.Dispersant is used to disperse negative pole toughener, and the mass ratio of itself and negative pole toughener is 0.15~0.25:1；
As further preferred scheme, positive pole thickener is consistent with the species of negative pole thickener, positive pole dispersant with The species of negative pole dispersant is consistent.
Liquefied mixture E modulus is less than two orders of magnitude of liquefied mixture B modulus；And liquefied mixture E modulus Less than two orders of magnitude of liquefied mixture D modulus.
Liquefied mixture E viscosity is less than two orders of magnitude of liquefied mixture B viscosity；And liquefied mixture E viscosity Less than two orders of magnitude of liquefied mixture D viscosity.
Liquefied mixture E is by PVDF-HFP, ionic liquid and Al2O3It is dissolved in NMP and ultrasound, stirring configuration obtains described Liquefied mixture E；Its configuration process is：
First PVDF-HFP is added in NMP, 55~65 DEG C, preferably 60 DEG C of heating water baths dissolve it, then addition Then ionic liquid adds Al to strengthen its electric conductivity2O3Nanometer powder, 1~2h of ultrasound, makes it be uniformly dispersed；Wherein PVDF- The mass ratio of HFP and ionic liquid is 1:1, PVDF-HFP and NMP mass ratio is 1:8~1:12, NMP and Al2O3Mass ratio should Choose 1:10~1:15.
Preferably, ionic liquid is ionic liquid at room temperature, and when the battery developed is lithium ion battery, it is Ionic liquid containing lithium ion, but the battery developed be sodium-ion battery when, its be the ionic liquid containing sodium ion.
The present invention, all-solid-state flexible one electrochemical cell uses the preparation method of 3D printing；Comprise the steps：
Step one cutting
In flexible substrates by being sized cutting；Obtain being reserved with the groove of lug position；
Step 2 vacuum vapour deposition prepares collector
In the bottom aggradation positive pole fluid and negative current collector of the groove that lug position is reserved with obtained by step one；Carried The groove of collector；
Step 3
By design size, using 3D printing technique, step 2 the groove with collector in printing positive pole, negative pole； Then electrolyte is printed between a positive electrode and a negative electrode；After the completion of printing, dry, solidify, finally inject electrolyte, encapsulation, obtain All-solid-state flexible one electrochemical cell；
When printing positive pole, the initial elastic modulus of positive electrode ink used is more than 10000Pa and modulus of elasticity is higher than dissipation mould Amount；The critical shearing stress of the positive electrode ink is between 100~10000Pa；The positive electrode ink by positive active material, just Pole toughener, positive pole thickener, positive pole dispersant, positive pole solvent composition, the granularity of the positive active material are less than or equal to 10 Micron；The positive pole toughener is CNT；The positive pole thickener is selected from carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyl At least one of propyl cellulose；The positive pole dispersant is selected from cetyl trimethylammonium bromide (CTAB), dodecyl At least one of sodium sulphate (SDS), neopelex (SDBS)；In the positive electrode ink, positive active material with The mass ratio of deionized water is 1:3~4.5, it is preferably 1:3；The mass ratio of positive active material and positive pole toughener is 20:1~ 2:1st, the mass ratio of positive active material and positive pole thickener is 25:1~40:1；The mass ratio of dispersant and positive pole toughener is 0.15~0.25:1；The positive pole solvent is by water and ethanol by volume 3:1-2 is preferably 3:2 compositions；
When printing negative pole, the initial elastic modulus of negative electrode ink used is more than 10000Pa and modulus of elasticity is higher than dissipation mould Amount；The critical shearing stress of the negative electrode ink is between 100~10000Pa；The negative electrode ink is by negative electrode active material, negative Pole toughener, negative pole thickener, negative pole dispersant, negative pole solvent composition, the granularity of the negative electrode active material are less than or equal to 10 Micron；The negative pole toughener is CNT；The negative pole thickener is selected from carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyl At least one of propyl cellulose；The negative pole dispersant is selected from cetyl trimethylammonium bromide (CTAB), dodecyl At least one of sodium sulphate (SDS), neopelex (SDBS)；In the negative electrode ink, negative electrode active material with The mass ratio of deionized water is 1:3~4.5, it is preferably 1:3；The mass ratio of negative electrode active material and negative pole toughener is 20:1~ 2:1st, the mass ratio of negative electrode active material and negative pole thickener is 25:1~40:1；The mass ratio of dispersant and positive pole toughener is 0.15~0.25:1；The negative pole solvent is by water and ethanol by volume 3:1-2, preferably 3:2 compositions；
When printing electrolyte, the initial elastic modulus of electrolyte ink used is more than 100Pa, and modulus of elasticity is higher than dissipation Modulus, when shear rate is γ=1S-1When, viscosities il=101~102Pa·S；The modulus of the electrolyte ink is less than positive pole Two orders of magnitude of ink modulus, and two orders of magnitude of the modulus less than positive electrode ink modulus of electrolyte ink；The electrolysis The viscosity of matter ink is less than two orders of magnitude of positive electrode ink viscosity, and the viscosity of liquid electrolyte ink is less than liquefied mixture D Two orders of magnitude of viscosity；
The electrolyte ink is by PVDF-HFP, ionic liquid and Al2O3It is dissolved in NMP and ultrasound, stirring configuration is obtained； Its process is：
First PVDF-HFP is added in NMP, 50-65 DEG C of heating water bath dissolves it, then adds ionic liquid to increase Its strong electric conductivity, then adds Al2O3Nanometer powder, 1~2h of ultrasound, makes it be uniformly dispersed；Wherein PVDF-HFP and ionic liquid Mass ratio be 1:1, PVDF-HFP and NMP mass ratio is 1:8~1:12, NMP and Al2O3Mass ratio should choose 1:10~1: 15。
Liquefied mixture E (i.e. electrolyte ink) modulus and viscosity will be less than about two orders of magnitude of both positive and negative polarity ink, because Restriction effect is played to the electrolyte of rear printing for already present both positive and negative polarity, will not be because viscosity is slightly lower and showing for sinuous flow occurs As.
Preferably, the integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；In step one； With ultraviolet exposure machine, developer solution and ion etching machine required shape is etched in the flexible substrates for coating one layer of SU-8 photoresist The groove of shape, and wash away photoresist with acetone；The one kind of the flexible substrates in PI, PE, PET and PETE.
Preferably, the integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；In step one； A length of 2.8~the 8.4mm of flexible substrates selection of dimension, a width of 2.2~3.2mm, thickness are 0.6~3mm.
Preferably, the integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；In step one； The groove generally cuboid, in the upper left corner with a groove ear is extended at the lower right corner to connect basolateral surface.
Preferably, the integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；In step one； The cuboid groove deep 0.4mm~2.8mm, is separated by multiple parallel groove columns being interspersed.The design on proper grooves column, favorably In the integral electrochemical cell of all-solid-state flexible in use, while superior electrical performance is ensured, its structure is ensured as far as possible Flexibility and battery integrality.
In the present invention, the width of the positive pole fluid or negative current collector is 3D printing equipment needle point used in step 3 The integral multiple of internal diameter.
Preferably, the integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；In step one； The groove column leaves when being cutting, long 0.8~1.8mm, high 0.4mm~2.8mm.In industrial applications, single groove column Width is the integral multiple of 3D printing equipment needle point internal diameter used.Preferably, when 3D printing equipment needle point internal diameter used is At 200 μm, a width of 0.2mm on single groove column.
Preferably, the integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；In step one； Groove column number is 2~9.In industrial applications, the beeline on all groove columns to cell wall is 3D printing equipment pin used The integral multiple of sharp internal diameter, maximum distance is 3 times of beeline, and adjacent slot column spacing is 3 times of beeline.
It is used as further preferred scheme, when 3D printing equipment needle point internal diameter used is 200 μm, all groove columns to cell wall Beeline be 0.2mm, maximum distance is 0.6mm, adjacent slot column spacing 0.6mm.
It is respectively the first side wall, second sidewall, the 3rd side wall, the 4th side wall to define cuboid four side walls of groove；First side Wall is joined directly together with second sidewall, and the positive pole ear that plus plate current-collecting body extends is left between the first side wall and the 4th side wall；First The length of side wall is more than second sidewall and equal to the length of the 3rd side wall；
3rd side wall is joined directly together with the 4th side wall, leaves what negative current collector extended between second sidewall and the 3rd side wall Negative lug；The length of 3rd side wall is more than the 4th side wall, and equal to the length of the first side wall；
When 3D printing equipment needle point internal diameter used is 200 μm, in cuboid groove, count from left to right, odd number groove column is arrived The distance of the first side wall be 0.2mm, to the distance of the 3rd side wall be 0.6mm；The distance of even number groove column to the 3rd side wall is 0.2mm, the distance to the first side wall are 0.6mm.
Preferably, the integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；In step 2； The bottom aggradation positive pole fluid and negative current collector of the groove of lug position are reserved with step one gained with vacuum evaporation plating machine； To the groove with collector；
The plus plate current-collecting body is aluminium collector, is distributed in the groove column the week side of boss of consecutive intervals, and its long cell wall avris of near-end And the right wall side, and extend 1mm from upper left chamfered groove ear；
The negative current collector is copper current collector, is distributed in the groove column the week side of boss of the consecutive intervals adjacent with plus plate current-collecting body, And its long cell wall avris of near-end and left hand wall side, and extend 1mm from upper right chamfered groove ear；The positive and negative electrode collector is wide 0.2mm。
Preferably, the integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；The positive pole Active material is LiCoO2、Li2MnO4、LiFePO4Deng；The negative electrode active material is graphite, selenides, phosphide, sulfide Deng.The grain diameter of the negative or positive electrode active material is less than 10 μm, to prevent from blocking pin hole；Thin powder causes ion embedding Enter, deviate from passage become it is many, bang path shortens, raising high rate performance；Simultaneously take fine powder can make intergranular pore increase there is provided More cushion spaces, bulk strain effect reduces, cyclical stability enhancing.
The integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；The configuration of negative or positive electrode ink, First dispersant should be added in the mixed liquor of deionized water and ethanol, add CNT after stirring and dissolving, ultrasound 30~ After 120min, the stable carbon nano tube dispersion liquid that is uniformly dispersed is obtained, then active material is slowly added under agitation, is treated Stir after 30~60min, still under agitation, be slowly added to thickener.
The integral electrochemical cell of all-solid-state flexible of the present invention uses the preparation method of 3D printing；The initial bullet of positive pole and negative electrode ink Property modulus be all higher than 10000Pa, and modulus of elasticity should be higher than that dissipation modulus, to ensure when being acted on without external force, and ink can be as solidifying Gluey state equally maintains shape；The critical shearing stress of ink should be between 100~10000Pa, when external force is more than critical shear During stress, as stress increases, the modulus of elasticity of ink drastically declines, less than dissipation modulus, and ink can flow, to ensure to beat The fluency of print process；The viscosity of ink should quickly reduce with the increase of shear rate, when shear rate is γ=1S-1 When, viscosity is η=102~104PaS is optimal.
The present invention, all-solid-state flexible one electrochemical cell uses the preparation method of 3D printing；In step 3, by positive electrode ink, Negative electrode ink and electrolyte ink are attached separately in three syringes, by design size, using 3D printer successively by positive electrode ink It is printed upon with negative electrode ink on positive pole and negative current collector, forms multi-layered electrode；Electrolyte ink is printed upon multi-layered electrode again Between flexible substrates on, formed solid electrolyte；After drying, injection electrolyte treats it by solid electrolyte between both positive and negative polarity Fully absorb, packed in vacuum glove box with PDMS；Obtain the integral electrochemical cell of all-solid-state flexible.
The printer operating speed chooses 0.1-20mm s-1；The printer pressure chooses 25~65Psi；It is described to beat Machine needle cylinder needle point internal diameter is printed to choose 200 μm；The multi-layered electrode number of plies is 2~14 layers,.The increase of the number of plies can improve area energy Metric density.The electrolyte is 1M LiPF6 PC-DEC (1:1, v/v) solution or 1M LiPF6 PC-EC-DEC (1:4:5, V/v/v) solution.The amount for injecting electrolyte is preferably a small amount of.After i.e. it is fully absorbed by solid electrolyte, seen in solid electrolyte Less than substantial amounts of electrolyte.
The present invention, all-solid-state flexible one electrochemical cell uses the preparation method of 3D printing；Plus plate current-collecting body, negative pole currect collecting Body, anode electrode, the integral multiple that the width of negative electrode and solid electrolyte is printing device needle point internal diameter used.
Principle and advantage
The present invention devises a kind of integral electrochemical cell of all-solid-state flexible and its preparation method using 3D printing, in the present invention It is middle to be applied to 3D printing technique in the manufacture of the integral electrochemical cell of all-solid-state flexible, it is excellent without by conventional method assembled battery Electrochemical cell production technology, saves battery manufacturing process time.All-solid-state battery structure, flexible substrates, the three of the electrode of addition toughener Person, which coordinates, causes the battery reliability high, has a safety feature, certain flexural deformation can be born, available on wearable device.
The present invention is by designing and having prepared special positive electrode ink, negative electrode ink, electrolyte ink, and this is 3D printing Prepare the integral electrochemical cell of high-performance all-solid-state flexible and provide necessary condition.
Brief description of the drawings
Fig. 1 is the flexible substrates schematic diagram for having carved groove
Fig. 2 is flexible substrates bottom surface collector schematic diagram
Fig. 3 is 3D printing multilayer positive pole schematic diagram
Fig. 4 is 3D printing electrolyte schematic diagram
In figure marked as：
1- flexible substrates 2- groove 3- groove ear 4- grooves column 5- plus plate current-collecting body 6- negative current collector 7- syringe 8- multilayers Positive pole 9- multilayer negative pole 10- solid electrolytes
Embodiment
Below in conjunction with the accompanying drawings and case study on implementation is described further to the present invention.
3D printing all-solid-state flexible one electrochemical cell, its structure and step are as shown in Figure 1, Figure 2, Figure 3 and Figure 4.Such as Fig. 1 institutes Show, etched with ultraviolet exposure machine, developer solution and ion etching machine in the flexible substrates (1) for coating one layer of SU-8 photoresist The groove (2) of required shape, whole groove is in cuboid, is extended at the upper left corner and the lower right corner outside a groove ear (3), connection substrate Side surface, the multiple parallel groove columns (4) being interspersed stayed when whole groove is by cutting are separated；With vacuum evaporation plating machine in groove table Face deposition plus plate current-collecting body (5) and negative current collector (6)；The positive electrode ink and negative electrode ink configured is installed in 10ml's respectively In syringe (7), it is printed upon on plus plate current-collecting body (5) with negative current collector (6), is formed many in layers with 3D printer successively Layer positive pole (8) and multilayer negative pole (9)；Electrolyte ink is printed between multilayer positive pole (8) and multilayer negative pole (9), forms solid State electrolyte (10), after drying, is transferred them in the glove box full of argon gas, injects a small amount of electrolyte between both positive and negative polarity, Treat that it is fully absorbed by solid electrolyte, then packed with PDMS.
The flexible substrates are from PI, PE, PET and PETE etc..
A length of 2.8~the 8.4mm of flexible substrates selection of dimension, a width of 2.2~3.2mm, thickness are 0.6~3mm.
The cuboid groove deep 0.4mm~2.8mm.
The groove column 0.8~1.8mm of length, wide 0.2mm, high 0.4mm~2.8mm.
Groove column number is 2~9, all groove column cell wall 0.2mms long far from near-end, cell wall 0.6mm long from distal end, adjacent slot Column spacing 0.6mm.
The plus plate current-collecting body is aluminium collector, is distributed in the groove column the week side of boss of consecutive intervals, and its long cell wall avris of near-end And the right wall side, and extend 1mm from upper left chamfered groove ear.
The negative current collector is copper current collector, is distributed in the groove column the week side of boss of the consecutive intervals adjacent with plus plate current-collecting body, And its long cell wall avris of near-end and left hand wall side, and extend 1mm from upper right chamfered groove ear.
The wide 0.2mm of positive and negative electrode collector.
The negative or positive electrode ink is mixed by negative or positive electrode active material, toughener, thickener, dispersant and solvent Stirring is formed.
The positive active material is LiCoO2、Li2MnO4、LiFePO4Deng；The negative electrode active material is graphite, selenizing Thing, phosphide, sulfide etc..
The negative or positive electrode active material particle is no more than 10 μm；The toughener chooses CNT；The thickening Carboxymethyl cellulose, hydroxymethyl cellulose or hydroxypropyl cellulose are chosen in agent；The solvent chooses deionized water, ethanol；It is described Dispersant chooses CTAB, SDS, SDBS etc..
Dispersant, first should be added in the mixed liquor of deionized water and ethanol by the configuration of the negative or positive electrode ink, Added after stirring and dissolving after CNT, 30~120min of ultrasound, obtain the stable carbon nano tube dispersion liquid that is uniformly dispersed, then will Active material is slowly added under agitation, after 30~60min to be mixed, still under agitation, is slowly added to thickener. Deionized water and the volume ratio of ethanol are 3:2；Active material and the mass ratio of deionized water are 1:3；Active material and carbon nanometer The mass ratio of pipe is 20:1~2:1, content of carbon nanotubes is higher, and material flexibility is higher, but comparatively battery specific capacity has Declined；The mass ratio of CNT and dispersant is 5:1~3:1；The mass ratio of active material and thickener is 25:1~40: 1；
Syringe (7) pinhole diameter is 200 μm；The print speed chooses 0.1-20mm s-1。
The printer pressure chooses 25~65Psi.
The multilayer positive pole (7) or multilayer negative pole (8) number of plies are 2~14 layers.
PVDF-HFP, first should be added in NMP by the configuration of the electrolyte ink, and 60 DEG C of heating water baths make its quick Dissolving, then adds ionic liquid to strengthen its electric conductivity, then adds Al2O3Nanometer powder, 1~2h of ultrasound makes it scattered equal It is even.The mass ratio of PVDF-HFP and ionic liquid is 10:1, PVDF-HFP and NMP mass ratio is 1:8~1:12, NMP with Al2O3Mass ratio should choose 1:10~1:15.
The positive pole and negative electrode ink, its initial elastic modulus should be more than 10000Pa, and modulus of elasticity should be higher than that dissipation Modulus, to ensure that, when being acted on without external force, ink can maintain shape as gel state；The critical shearing stress of ink should be Between 100~10000Pa, when external force is more than critical shearing stress, stress increase therewith, the modulus of elasticity of ink drastically under Drop, less than dissipation modulus, ink can flow, to ensure the fluency of print procedure；The viscosity of ink should be with shear rate Increase and quickly reduce, when shear rate be γ=1S-1When, viscosity is η=102~104PaS is optimal
The electrolyte ink, its initial elastic modulus should be more than 100Pa, and modulus of elasticity should be higher than that dissipation modulus, To ensure that, when being acted on without external force, ink can maintain shape as gel state；When exposed to external forces, as stress increases, The modulus of elasticity of ink drastically declines, less than dissipation modulus, and ink can flow, to ensure the fluency of print procedure；Ink Viscosity should quickly reduce with the increase of shear rate, when shear rate be γ=1S-1When, viscosity is η=101~ 102PaS is optimal.The modulus and viscosity of electrolyte ink will be less than about two orders of magnitude of both positive and negative polarity ink, because already present Both positive and negative polarity plays restriction effect to the electrolyte of rear printing, and electrolyte will not be because viscosity is slightly lower and the phenomenon of sinuous flow occurs.
The electrolyte uses the electric electrolyte of lithium of commercialization, such as 1M LiPF6PC-DEC (1:1, v/v) solution Or 1M LiPF6PC-EC-DEC (1:4:5, v/v/v) solution etc., addition is preferred with 300 microlitres~1000 microlitres.
Embodiment 1
S1, cutting
Raw material：Photoresist SU-8, developer solution, acetone
Equipment：Ultraviolet exposure machine, sol evenning machine, heating plate, plasma etching machine
Preparation technology：Flexible substrates are carried out to 8min front baking with heating plate, 180 DEG C of temperature is set, then is existed with sol evenning machine Uniform one layer of SU-8 photoresist of coating in flexible substrates, the flexible substrates being coated with after photoresist is carried out 8min rear baking, Temperature is still 180 DEG C,；Flexible substrates are covered with the shadow shield of size identical with non-groove base part shown in figure one, by ultraviolet Exposure machine irradiates after 6s, developer solution immersion 13s, then etches flexible substrates, the region quilt of exposure with plasma etching machine (ICP) Etch away, then wash away photoresist with acetone, obtain being reserved with the cuboid groove of lug position.The flexible substrates are PI；Its Length is 4.4mm, and a width of 1.8mm, thickness is 1.4mm.The cuboid groove deep 1mm.4 grooves are left in the cuboid groove Column, along groove column length direction, the distance of groove column near-end to cell wall is that (that is, the beeline of groove column to cell wall is 0.2mm 0.2mm), distally distance is 0.6mm (i.e. the longest distance of groove column to cell wall is 0.6mm), adjacent slot column spacing 0.6mm；It is single It is a width of 0.2mm in groove column, high in groove depth；It is 1mm that lug, which reserves width,；
It is respectively the first side wall, second sidewall, the 3rd side wall, the 4th side wall to define cuboid four side walls of groove；First side Wall is joined directly together with second sidewall, and the positive pole ear that plus plate current-collecting body extends is left between the first side wall and the 4th side wall；First The length of side wall is more than second sidewall and equal to the length of the 3rd side wall；
3rd side wall is joined directly together with the 4th side wall, leaves what negative current collector extended between second sidewall and the 3rd side wall Negative lug；The length of 3rd side wall is more than the 4th side wall, and equal to the length of the first side wall；
In cuboid groove, count from left to right, the distance on odd number groove column to the first side wall is for 0.2mm, to the 3rd side wall Distance is 0.6mm；The distance of even number groove column to the 3rd side wall is that 0.2mm, the distance to the first side wall are 0.6mm；
S2, vacuum vapour deposition prepares collector
Raw material：Aluminium, copper
Equipment：Light microscope, vacuum evaporation plating machine
Preparation technology：Observe under an optical microscope, with the bottom land of vacuum evaporation plating machine flexible substrates according to the shape shown in Fig. 2 Shape deposition of aluminum and copper are respectively as plus plate current-collecting body and negative current collector；The flexible substrates after collector will have been plated and dress is immersed in Have in the beaker of acetone, shake a moment, remove photoresist and unnecessary metallic aluminium, copper.
The plus plate current-collecting body is aluminium collector, after evaporation, and plus plate current-collecting body is along the first side wall, second sidewall and odd number The bottom on number groove column be distributed in uniform ribbon and positioned at second sidewall bottom plus plate current-collecting body to the most short distance to the 3rd side wall From for 0.2mm, to ensure that plus plate current-collecting body is not contacted with negative current collector；The width of plus plate current-collecting body is 0.2mm；
From upper left, chamfered groove ear extends 1mm after evaporation, as lug.
The negative current collector is copper current collector, after evaporation, and negative current collector is along the 3rd side wall, the 4th side wall and even number The bottom on number groove column is distributed in uniform ribbon and is to the distance to the first side wall positioned at the negative current collector of the 4th sidewall bottom 0.2mm, to ensure that plus plate current-collecting body is not contacted with negative current collector；The width of negative current collector is 0.2mm；
Extend 1mm from upper right chamfered groove ear after evaporation；As lug.
S3, prepares positive pole, negative pole and electrolyte ink
Raw material：Positive active material uses cobalt acid lithium, and negative electrode active material uses graphite；Toughener is more using graphitization Wall carbon nano tube；Thickener uses carboxymethyl cellulose；Solvent chooses CTAB from deionized water and ethanol, dispersant.
Equipment：Magnetic stirrer, electromagnetic agitation thermostat water bath
Preparation technology：
9.84mg dispersing agent Cs TAB is first added to 9ml deionized waters with the mixed liquor of 6ml ethanol, adding after stirring and dissolving Plus 360mg CNTs, after ultrasonic 60min, the stable carbon nano tube dispersion liquid that is uniformly dispersed is obtained, then 3g cobalt acid lithiums are being stirred It is slowly added in the case of mixing, after 30min to be mixed, still under agitation, is slowly added to 180mg thickener carboxymethyl celluloses Element, electromagnetic agitation stirring 24h, after partial solvent volatilization, is placed at 50 DEG C and is stirred, more multi-solvent is volatilized, finally The state of ink is obtained, its initial elastic modulus is 74250Pa, and modulus of elasticity should be higher than that dissipation modulus, to ensure without outer Masterpiece used time, ink can maintain shape as gel state；The critical shearing stress of ink is 206Pa, when external force is more than this During critical shearing stress, as stress increases, the modulus of elasticity of ink drastically declines, less than dissipation modulus, and ink can flow, It ensure that the fluency of print procedure；The viscosity of ink should quickly reduce with the increase of shear rate, when shear rate is γ=1S-1When, viscosity is η=5590PaS, conveniently.
9.84mg dispersing agent Cs TAB is first added to 9ml deionized waters with the mixed liquor of 6ml ethanol, adding after stirring and dissolving Plus 360mg CNTs, after ultrasonic 60min, the stable carbon nano tube dispersion liquid that is uniformly dispersed is obtained, then by 3g graphite in stirring In the case of be slowly added to, after 30min to be mixed, still under agitation, be slowly added to 135mg thickener carboxymethyl celluloses, Electromagnetic agitation stirs 24h, after partial solvent volatilization, is placed at 50 DEG C and is stirred, more multi-solvent is volatilized, finally give The state of ink, its initial elastic modulus is 51774Pa, and modulus of elasticity is higher than dissipation modulus, when being acted on without external force, ink Shape can be maintained as gel state；The critical shearing stress of ink is 195Pa, when external force is more than this critical shearing stress When, as stress increases, the modulus of elasticity of ink drastically declines, less than dissipation modulus, and ink starts flowing, it is ensured that printed The fluency of journey；The viscosity of ink should quickly reduce with the increase of shear rate, when shear rate is γ=1S-1When, glue Spend for η=5207PaS, conveniently.
0.2971gPVDF-HFP is added in 3gNMP, 60 DEG C of heating water baths make it quickly dissolve, then addition Then 0.03g ionic liquids add 3gAl to strengthen its electric conductivity2O3Nanometer powder, ultrasonic 1.5h, makes it be uniformly dispersed.It is described Electrolyte ink, its initial elastic modulus is 1041Pa, and modulus of elasticity is higher than dissipation modulus, when being acted on without external force, ink Shape can be maintained as gel state；When exposed to external forces, as stress increases, the modulus of elasticity of ink drastically declines, low In dissipation modulus, ink starts flowing, it is ensured that the fluency of print procedure；The viscosity of ink is with the increase of shear rate It is quick to reduce, when shear rate is γ=1S-1When, viscosity is η=78PaS, conveniently.Electrolyte ink, which is printed on, has deposited Both positive and negative polarity between, due to the restriction effect of both positive and negative polarity, electrolyte is because viscosity is slightly lower and the phenomenon of sinuous flow occurs.
S4,3D printing battery
Raw material：Graphite ink made from step S2, the PC-DEC of cobalt acid lithium ink, electrolyte ink and 1M LiPF6 (1:1, v/v) electrolyte；
Equipment：3D printer, vacuum glove box
Preparation technology：
Cobalt acid lithium ink, Graphite ink and electrolyte ink are respectively charged into three capacity 10ml, 200 μm of needle aperture In needle tubing, the needle tubing that first will be equipped with cobalt acid lithium ink is installed, and sets syringe needle from collection liquid surface 0.1mm, print speed 8.5mm/s, printer pressure 56Psi, syringe needle is moved according to the print routine set, continuously 5 layers of positive pole of printing, positive pole Width is consistent with the width of plus plate current-collecting body；Then the needle tubing equipped with Graphite ink is changed, syringe needle is set from collection liquid surface 0.1mm, print speed 6.5mm/s, printer pressure 51Psi, syringe needle is moved according to the print routine set, continuous printing 5 layers of negative pole, the width of negative pole is consistent with the width of negative current collector；The needle tubing equipped with electrolyte ink is changed afterwards, and setting is beaten Print-out rate 10mm/s, printer pressure 31Psi, by electrolyte printing between a positive electrode and a negative electrode, form solid electrolyte；It will beat Printed battery is placed in vacuum drying chamber, is dried after 24h, is injected in the glove box full of argon gas with liquid-transfering gun at 60 DEG C 400 microlitres of 1M LiPF6 PC-DEC (1:1, v/v) electrolyte treats that it is fully absorbed by solid electrolyte between both positive and negative polarity, Packed again with PDMS.Have benefited from the pliability of CNT, and solid electrolyte membrane possesses certain flexibility in itself, in addition base Bottom and packaging are flexibility, and this all-solid-state battery possesses flexibility.
Its electric property is detected, it is found that its electric property is excellent.
Embodiment 2
S1, cutting
The uniform embodiment 1 of other conditions is consistent, and difference is that substrate is PET；
S2, vacuum vapour deposition prepares collector
It is completely consistent with the step of embodiment 1
S3, prepares positive pole, negative pole and electrolyte ink
Raw material：Positive active material uses cobalt acid lithium, and negative electrode active material uses graphite；Toughener is more using graphitization Wall carbon nano tube；Thickener uses carboxymethyl cellulose；Solvent chooses CTAB from deionized water and ethanol, dispersant.
Equipment：Magnetic stirrer, electromagnetic agitation thermostat water bath
Preparation technology：
9.84mg dispersing agent Cs TAB is first added to 9ml deionized waters with the mixed liquor of 6ml ethanol, adding after stirring and dissolving Plus 45mg CNTs, after ultrasonic 60min, the stable carbon nano tube dispersion liquid that is uniformly dispersed is obtained, then 3g cobalt acid lithiums are being stirred It is slowly added in the case of mixing, after 30min to be mixed, still under agitation, is slowly added to 180mg thickener carboxymethyl celluloses Element, electromagnetic agitation stirring 24h, after partial solvent volatilization, is placed at 50 DEG C and is stirred, more multi-solvent is volatilized, finally The state of ink is obtained, its initial elastic modulus is 58358Pa, and modulus of elasticity is higher than dissipation modulus, when being acted on without external force, Ink can maintain shape as gel state；The critical shearing stress of ink is 188Pa, when external force should more than this critical shear During power, as stress increases, the modulus of elasticity of ink drastically declines, less than dissipation modulus, and ink starts flowing, it is ensured that printing The fluency of process；The viscosity of ink should quickly reduce with the increase of shear rate, when shear rate is γ=1S-1When, Viscosity is η=4520PaS, conveniently.
9.84mg dispersing agent Cs TAB is first added to 9ml deionized waters with the mixed liquor of 6ml ethanol, adding after stirring and dissolving Plus 45mg CNTs, after ultrasonic 60min, the stable carbon nano tube dispersion liquid that is uniformly dispersed is obtained, then by 3g graphite in stirring In the case of be slowly added to, after 30min to be mixed, still under agitation, be slowly added to 135mg thickener carboxymethyl celluloses, Electromagnetic agitation stirs 24h, after partial solvent volatilization, is placed at 50 DEG C and is stirred, more multi-solvent is volatilized, finally give The state of ink, its initial elastic modulus is 54491Pa, and modulus of elasticity is higher than dissipation modulus, when being acted on without external force, ink Shape can be maintained as gel state；The critical shearing stress of ink is 182Pa, when external force is more than this critical shearing stress When, as stress increases, the modulus of elasticity of ink drastically declines, less than dissipation modulus, and ink starts flowing, it is ensured that printed The fluency of journey；The viscosity of ink should quickly reduce with the increase of shear rate, when shear rate is γ=1S-1When, glue Spend for η=4244PaS, conveniently.
0.2993gPVDF-HFP is added in 3gNMP, 60 DEG C of heating water baths make it quickly dissolve, then addition Then 0.03g ionic liquids add 3gAl to strengthen its electric conductivity2O3Nanometer powder, ultrasonic 1.5h, makes it be uniformly dispersed.It is described Electrolyte ink, its initial elastic modulus is 1088Pa, and modulus of elasticity is higher than dissipation modulus, when being acted on without external force, ink Shape can be maintained as gel state；When exposed to external forces, as stress increases, the modulus of elasticity of ink drastically declines, low In dissipation modulus, ink starts flowing, it is ensured that the fluency of print procedure；The viscosity of ink is with the increase of shear rate It is quick to reduce, when shear rate is γ=1S-1When, viscosity is η=82PaS, conveniently.Electrolyte ink, which is printed on, has deposited Both positive and negative polarity between, due to the restriction effect of both positive and negative polarity, electrolyte is because viscosity is slightly lower and the phenomenon of sinuous flow occurs.
S4,3D printing battery
Raw material：Graphite ink made from step S2, the PC-DEC of cobalt acid lithium ink, electrolyte ink and 1M LiPF6 (1:1, v/v) electrolyte
Equipment：3D printer, vacuum glove box
Preparation technology：
Cobalt acid lithium ink, Graphite ink and electrolyte ink are respectively charged into three capacity 10ml, 200 μm of needle aperture In needle tubing, the needle tubing that first will be equipped with cobalt acid lithium ink is installed, and sets syringe needle from collection liquid surface 0.1mm, print speed 5.5mm/s, printer pressure 50Psi, syringe needle is moved according to the print routine set, continuously 5 layers of positive pole of printing；Then more Changing the outfit has the needle tubing of Graphite ink, sets syringe needle from collection liquid surface 0.1mm, print speed 4.5mm/s, printer pressure 43Psi, syringe needle is moved according to the print routine set, continuously 5 layers of negative pole of printing；Change afterwards equipped with electrolyte ink Needle tubing, sets print speed 10mm/s, printer pressure 33Psi, by electrolyte printing between a positive electrode and a negative electrode, forms solid-state Electrolyte；Printed battery is placed in vacuum drying chamber, dries after 24h, is used in the glove box full of argon gas at 60 DEG C Liquid-transfering gun injects 400 microlitres of 1M LiPF6 PC-DEC (1:1, v/v) electrolyte treats it by solid electrolyte between both positive and negative polarity Fully absorb, then packed with PDMS.This all-solid-state battery possesses flexibility, but flexible not high.
Comparative example 1
S1, cutting
It is completely consistent with the step of embodiment 1
S2, vacuum vapour deposition prepares collector
It is completely consistent with the step of embodiment 1
S3, prepares positive pole, negative pole and electrolyte ink
Raw material：Positive active material uses cobalt acid lithium, and negative electrode active material uses graphite；Toughener is more using graphitization Wall carbon nano tube；Thickener uses carboxymethyl cellulose；Solvent chooses CTAB from deionized water and ethanol, dispersant.
Equipment：Magnetic stirrer, electromagnetic agitation thermostat water bath
Preparation technology：
9.84mg dispersing agent Cs TAB is first added to 9ml deionized waters with the mixed liquor of 6ml ethanol, adding after stirring and dissolving Plus 360mg CNTs, after ultrasonic 60min, the stable carbon nano tube dispersion liquid that is uniformly dispersed is obtained, then 3g cobalt acid lithiums are being stirred It is slowly added in the case of mixing, after 30min to be mixed, still under agitation, is slowly added to 300mg thickener carboxymethyl celluloses Element, electromagnetic agitation stirring 24h, after partial solvent volatilization, is placed at 50 DEG C and is stirred, more multi-solvent is volatilized, finally The state of ink is obtained, its initial elastic modulus is 2300Pa, and modulus of elasticity is less than dissipation modulus, when being acted on without external force, Ink can not maintain shape.
9.84mg dispersing agent Cs TAB is first added to 9ml deionized waters with the mixed liquor of 6ml ethanol, adding after stirring and dissolving Plus 360mg CNTs, after ultrasonic 60min, the stable carbon nano tube dispersion liquid that is uniformly dispersed is obtained, then by 3g graphite in stirring In the case of be slowly added to, after 30min to be mixed, still under agitation, be slowly added to 250mg thickener carboxymethyl celluloses, Electromagnetic agitation stirs 24h, after partial solvent volatilization, is placed at 50 DEG C and is stirred, more multi-solvent is volatilized, finally give The state of ink, its initial elastic modulus is 2026Pa, and modulus of elasticity is less than dissipation modulus, when being acted on without external force, ink Shape can not be maintained.
0.3007gPVDF-HFP is added in 3gNMP, 60 DEG C of heating water baths make it quickly dissolve, then addition Then 0.03g ionic liquids add 3gAl to strengthen its electric conductivity2O3Nanometer powder, ultrasonic 1.5h, makes it be uniformly dispersed.It is described Electrolyte ink, its initial elastic modulus is 1095Pa, and modulus of elasticity is higher than dissipation modulus, when being acted on without external force, ink Shape can be maintained as gel state；When exposed to external forces, as stress increases, the modulus of elasticity of ink drastically declines, low In dissipation modulus, ink starts flowing, it is ensured that the fluency of print procedure；The viscosity of ink is with the increase of shear rate It is quick to reduce, when shear rate is γ=1S-1When, viscosity is η=84PaS, conveniently.
S4,3D printing battery
Raw material：Graphite ink made from step S2, the PC-DEC of cobalt acid lithium ink, electrolyte ink and 1M LiPF6 (1:1, v/v) electrolyte
Equipment：3D printer, vacuum glove box
Preparation technology：
Cobalt acid lithium ink, Graphite ink and electrolyte ink are respectively charged into three capacity 10ml, 200 μm of needle aperture In needle tubing, the needle tubing that first will be equipped with cobalt acid lithium ink is installed, and sets syringe needle from collection liquid surface 0.1mm, print speed 11.5mm/s, printer pressure 27Psi, syringe needle is moved according to the print routine set, continuously 5 layers of positive pole of printing, structure It can not stablize；Then the needle tubing equipped with Graphite ink is changed, syringe needle is set from collection liquid surface 0.1mm, print speed 13mm/s, Printer pressure 25Psi, syringe needle is moved according to the print routine set, continuously 5 layers of negative pole of printing, and structure can not be stablized, All-solid-state battery printing failure.

Claims (10)

1. all-solid-state flexible one electrochemical cell, it is characterised in that：Including soft shell, flexible positive pole, flexible negative pole, flexible solid Electrolyte；
The flexible positive pole includes plus plate current-collecting body and flexible solid substance A；The flexible solid substance A is by liquefied mixture B Obtained after drying process, the initial elastic modulus of the liquefied mixture B is more than 10000Pa and modulus of elasticity is higher than dissipation Modulus；The critical shearing stress of the liquefied mixture B is between 100~10000Pa；The liquefied mixture B is lived by positive pole Property material, positive pole toughener, positive pole thickener, positive pole dispersant, positive pole solvent composition, the granularity of the positive active material is small In equal to 10 microns；
The flexible negative pole includes negative current collector and flexible solid substance C；The flexible solid substance C is by liquefied mixture D Obtained after drying process, the initial elastic modulus of the liquefied mixture D is more than 10000Pa and modulus of elasticity is higher than dissipation Modulus；The critical shearing stress of the liquefied mixture D is between 100~10000Pa；The liquefied mixture D is lived by negative pole Property material, negative pole toughener, negative pole thickener, negative pole dispersant, negative pole solvent composition, the granularity of the negative electrode active material is small In equal to 10 microns；
Flexible solid electrolyte is obtained by liquefied mixture E after drying process, the initial elastic modulus of the liquefied mixture E More than 100Pa, and modulus of elasticity is higher than dissipation modulus, when shear rate is γ=1S-1When, viscosities il=101~102Pa·S。
2. the integral electrochemical cell of all-solid-state flexible according to claim 1, it is characterised in that：
The positive pole toughener, negative pole toughener are CNT；
The positive pole thickener, negative pole thickener in carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose extremely Few one kind；
The positive pole dispersant, negative pole dispersant are selected from cetyl trimethylammonium bromide, lauryl sodium sulfate, dodecyl At least one of benzene sulfonic acid sodium salt.
3. the integral electrochemical cell of all-solid-state flexible according to claim 1, it is characterised in that：
In liquefied mixture B, the mass ratio of positive active material and deionized water is 1:3~4.5；Positive active material and positive pole The mass ratio of toughener is 20:1~2:1；The mass ratio of active material and positive pole thickener is 25:1~40:1；Dispersant is used for Scattered positive pole toughener, the mass ratio of itself and positive pole toughener is 0.15~0.25:1；
The positive pole solvent is by water and ethanol by volume 3:2~3:1 composition；
The negative pole solvent is by water and ethanol by volume 3:2~3:1 composition；
In liquefied mixture D, the mass ratio of negative electrode active material and deionized water is 1:3~4.5；Negative electrode active material and negative pole The mass ratio of toughener is 20:1~2:1st, the mass ratio of negative electrode active material and negative pole thickener is 25:1~40:1；Dispersant For disperseing negative pole toughener, the mass ratio of itself and negative pole toughener is 0.15~0.25:1.
4. the integral electrochemical cell of all-solid-state flexible according to claim 1, it is characterised in that：
Liquefied mixture E modulus is less than two orders of magnitude of liquefied mixture B modulus；And liquefied mixture E modulus is less than Two orders of magnitude of liquefied mixture D modulus；
Liquefied mixture E viscosity is less than two orders of magnitude of liquefied mixture B viscosity；And liquefied mixture E viscosity is less than Two orders of magnitude of liquefied mixture D viscosity.
5. the integral electrochemical cell of all-solid-state flexible according to claim 1, it is characterised in that：
Liquefied mixture E is by PVDF-HFP, ionic liquid and Al2O3It is dissolved in NMP and ultrasound, stirring configuration obtains the liquid Mixture E；Its configuration process is：
PVDF-HFP is first added to 55~65 DEG C of heating water baths in NMP, it is dissolved, then adds ionic liquid to strengthen it Electric conductivity, then adds Al2O3Nanometer powder, 1~2h of ultrasound, makes it be uniformly dispersed；Wherein PVDF-HFP and ionic liquid matter Amount is than being 1:1, PVDF-HFP and NMP mass ratio is 1:8~1:12, NMP and Al2O3Mass ratio should choose 1:10~1:15.
6. all-solid-state flexible one electrochemical cell uses the preparation method of 3D printing；It is characterized in that comprising the steps：
Step one cutting
In flexible substrates by being sized cutting；Obtain being reserved with the groove of lug position；
Step 2 vacuum vapour deposition prepares collector
In the bottom aggradation positive pole fluid and negative current collector of the groove that lug position is reserved with obtained by step one；Obtain carrying afflux The groove of body；
Step 3
By design size, using 3D printing technique, step 2 the groove with collector in printing positive pole, negative pole；Then Electrolyte is printed between a positive electrode and a negative electrode；After the completion of printing, dry, solidify, finally inject electrolyte, encapsulation, obtain entirely solid State integrated flexible battery；
When printing positive pole, the initial elastic modulus of positive electrode ink used is more than 10000Pa and modulus of elasticity is higher than dissipation modulus； The critical shearing stress of the positive electrode ink is between 100~10000Pa；The positive electrode ink is by positive active material, positive pole Toughener, positive pole thickener, positive pole dispersant, positive pole solvent composition, the granularity of the positive active material are micro- less than or equal to 10 Rice；The positive pole toughener is CNT；The positive pole thickener is selected from carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl At least one of base cellulose；The positive pole dispersant is selected from cetyl trimethylammonium bromide, lauryl sodium sulfate, ten At least one of dialkyl benzene sulfonic acids sodium；In the positive electrode ink, the mass ratio of positive active material and deionized water is 1:3 ~4.5；The mass ratio of positive active material and positive pole toughener is 20:1~2:1st, positive active material and positive pole thickener Mass ratio is 25:1~40:1；The mass ratio of dispersant and positive pole toughener is 0.15~0.25:1；The positive pole solvent is by water With ethanol by volume 3:2~3:1 composition；
When printing negative pole, the initial elastic modulus of negative electrode ink used is more than 10000Pa and modulus of elasticity is higher than dissipation modulus； The critical shearing stress of the negative electrode ink is between 100~10000Pa；The negative electrode ink is by negative electrode active material, negative pole Toughener, negative pole thickener, negative pole dispersant, negative pole solvent composition, the granularity of the negative electrode active material are micro- less than or equal to 10 Rice；The negative pole toughener is CNT；The negative pole thickener is selected from carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl At least one of base cellulose；The negative pole dispersant is selected from cetyl trimethylammonium bromide, lauryl sodium sulfate, ten At least one of dialkyl benzene sulfonic acids sodium；In the negative electrode ink, the mass ratio of negative electrode active material and deionized water is 1:3 ~4.5；The mass ratio of negative electrode active material and negative pole toughener is 20:1~2:1st, negative electrode active material and negative pole thickener Mass ratio is 25:1~40:1；The mass ratio of dispersant and negative pole toughener is 0.15~0.25:1；The negative pole solvent is by water With ethanol by volume 3:2~3:1 composition；
When printing electrolyte, the initial elastic modulus of electrolyte ink used is more than 100Pa, and modulus of elasticity is higher than dissipation mould Amount, when shear rate is γ=1S-1When, viscosities il=101~102Pa·S；The modulus of the electrolyte ink is less than positive pole ink Two orders of magnitude of water modulus, and two orders of magnitude of the modulus less than positive electrode ink modulus of electrolyte ink；The electrolyte The viscosity of ink is less than two orders of magnitude of positive electrode ink viscosity, and the viscosity of liquid electrolyte ink is less than negative electrode ink viscosity Two orders of magnitude；
The electrolyte ink is by PVDF-HFP, ionic liquid and Al2O3It is dissolved in NMP and ultrasound, stirring configuration is obtained；Its mistake Cheng Wei：
First PVDF-HFP is added in NMP, 50~65 DEG C of heating water baths dissolve it, then adds ionic liquid to strengthen Its electric conductivity, then adds Al2O3Nanometer powder, 1~2h of ultrasound, makes it be uniformly dispersed；Wherein PVDF-HFP and ionic liquid Mass ratio is 1:1, PVDF-HFP and NMP mass ratio is 1:8~1:12, NMP and Al2O3Mass ratio should choose 1:10~1:15.
7. the integral electrochemical cell of all-solid-state flexible according to claim 5 uses the preparation method of 3D printing；It is characterized in that：
In step one；The flexible substrates of one layer of SU-8 photoresist are being coated with ultraviolet exposure machine, developer solution and ion etching machine On etch needed for shape groove, and wash away photoresist with acetone；The flexible substrates are from one in PI, PE, PET, PETE Kind；
The thickness of the flexible substrates is 0.6~3mm；
In the groove etched, groove column is also distributed with；The beeline of the groove column to cell wall is equal to 1 times of positive pole fluid or negative pole The width of collector, the longest distance on the groove column to cell wall is equal to the width of 3 times of positive pole fluids or negative current collector；It is described just The width of pole fluid or negative current collector is the integral multiple of 3D printing equipment needle point internal diameter used in step 3.
8. the integral electrochemical cell of all-solid-state flexible according to claim 7 uses the preparation method of 3D printing；It is characterized in that： The groove generally cuboid,
In the upper left corner with a groove ear is extended at the lower right corner to connect basolateral surface；
The cuboid groove deep 0.4mm~2.8mm, is separated by multiple parallel groove columns being interspersed；
The groove column leaves when being cutting, a length of 0.8~1.8mm on single groove column, a height of 0.4mm~2.8mm；As 3D used When printing device needle point internal diameter is 200 μm, a width of 0.2mm on single groove column；
Groove column number is 2~9, when 3D printing equipment needle point internal diameter used is 200 μm, all groove columns to the most short of cell wall Distance is 0.2mm, and maximum distance is 0.6mm, adjacent slot column spacing 0.6mm；
It is respectively the first side wall, second sidewall, the 3rd side wall, the 4th side wall to define cuboid four side walls of groove；The first side wall with Second sidewall is joined directly together, and the positive pole ear that plus plate current-collecting body extends is left between the first side wall and the 4th side wall；The first side wall Length be more than second sidewall and equal to the 3rd side wall length；
3rd side wall is joined directly together with the 4th side wall, and the negative pole that negative current collector extends is left between second sidewall and the 3rd side wall Lug；The length of 3rd side wall is more than the 4th side wall, and equal to the length of the first side wall；
When 3D printing equipment needle point internal diameter used is 200 μm, in cuboid groove, count from left to right, odd number groove column to first The distance of side wall be 0.2mm, to the distance of the 3rd side wall be 0.6mm；Even number groove column to the 3rd side wall distance for 0.2mm, Distance to the first side wall is 0.6mm.
9. the integral electrochemical cell of all-solid-state flexible according to claim 8 uses the preparation method of 3D printing；It is characterized in that： In step 2；The bottom aggradation positive pole fluid and negative pole of the groove of lug position are reserved with step one gained with vacuum evaporation plating machine Collector；Obtain the groove with collector；The wide 0.2mm of positive and negative electrode collector；
The plus plate current-collecting body is aluminium collector, after evaporation, and plus plate current-collecting body is along the first side wall, second sidewall and odd number groove The bottom on column is distributed in uniform ribbon and the plus plate current-collecting body positioned at second sidewall bottom is to the distance to the 3rd side wall From upper left, chamfered groove ear extends 1mm after 0.4mm, evaporation, as lug；
The negative current collector is copper current collector, after evaporation, and negative current collector is along the 3rd side wall, the 4th side wall and even number groove The bottom on column is distributed in uniform ribbon and is to the distance to the first side wall positioned at the negative current collector of the 4th sidewall bottom 0.4mm, the width of negative current collector is to extend 1mm from upper right chamfered groove ear after 0.2mm, evaporation；As lug.
10. the integral electrochemical cell of all-solid-state flexible according to claim 5 uses the preparation method of 3D printing；Its feature exists In：
The positive active material is selected from LiCoO2、Li2MnO4、LiFePO4In one kind；
The one kind of the negative electrode active material in graphite, selenides, phosphide, sulfide；
In step 3, positive electrode ink, negative electrode ink and electrolyte ink are attached separately in three syringes, by design size, profit Positive electrode ink and negative electrode ink are printed upon on positive pole and negative current collector successively with 3D printer, multi-layered electrode is formed；Again will Electrolyte ink is printed upon in the flexible substrates between multi-layered electrode, forms solid electrolyte；After drying, injection electrolyte is in positive and negative Between pole, treat that it is fully absorbed by solid electrolyte, packed in vacuum glove box with PDMS；Obtain all-solid-state flexible integration Battery；The printer operating speed chooses 0.1-20mm s-1；The printer pressure chooses 25~65Psi；The printer Syringe needle point internal diameter is 200 μm；The multi-layered electrode number of plies is 2~14 layers.
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