CN106532109A - All-solid-state lithium-ion battery and manufacturing method thereof - Google Patents
All-solid-state lithium-ion battery and manufacturing method thereof Download PDFInfo
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- CN106532109A CN106532109A CN201611237951.6A CN201611237951A CN106532109A CN 106532109 A CN106532109 A CN 106532109A CN 201611237951 A CN201611237951 A CN 201611237951A CN 106532109 A CN106532109 A CN 106532109A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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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- 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 invention discloses an all-solid-state lithium-ion battery and a manufacturing method thereof. The manufacturing method comprises the following steps of (1) dissolving a polymer electrolyte into a solvent to prepare a glue solution; (2) fully mixing a positive electrode host material, a conductive agent and the glue solution obtained in the step (1), coating a positive current collector, heating the positive current collector and then carrying out co-curing to obtain a positive electrode plate, fully mixing a negative electrode host material, the conductive agent and the glue solution obtained in the step (1), coating a negative current collector, heating the negative current collector and then carrying out co-curing to obtain a negative electrode roll; (3) carrying out mechanical ball milling on a sulfide electrolyte, dissolving the product into the solvent to prepare slurry, coating the surface of the negative electrode roll, heating the negative electrode roll and then curing the negative electrode roll to obtain a negative electrode plate; and (4) assembling the positive electrode plate and the negative electrode plate by adopting a lamination technology to obtain the all-solid-state lithium-ion battery. Compared with the prior art, the all-solid-state lithium-ion battery disclosed by the invention has relatively low DC resistance, relatively high ionic conductivity and good cycle performance.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of all-solid lithium-ion battery and preparation method thereof.
Background technology
Lithium ion battery is because which is lightweight, specific energy/specific power height, few self discharge, life-span length the features such as be considered most
One of electrochemical energy storage technology of competitiveness.Current commercial li-ion battery widely uses liquid electrolyte, is characterized in tool
Standby higher electrical conductivity and excellent chemical property.But, the flash point of liquid electrolyte is relatively low, in heavy-current discharge, mistake
Electrolyte may be caused when degree chargings, the abnormal conditions such as internal short-circuit to generate heat spontaneous combustion, or even the safety problem such as set off an explosion.And make
With the all-solid-state battery of solid electrolyte, then safety is greatly improved, and battery safety device can be simplified, reduce being manufactured into
This.Thus the research of all-solid lithium-ion battery is just attracting increasing concern.
The solid electrolyte for having developed at present is broadly divided into two classes：Inorganic electrolyte and polymer dielectric.Nothing
Machine electrolyte can be further separated into as two class of sulfide and oxide.Sulfide has higher ionic conductivity.However, sulfuration
Thing solid electrolyte there is also some shortcomings in the application, in electrode/solid electrolyte interface, due to acting between oxygen-lithium ion
Power is eager to excel a lot than sulfur-lithium ion intermolecular forces, and when oxide anode belongs to, to be provided simultaneously with ionic conduction mixed with electronic conduction
When closing conductor, space charge layer will be produced at electrode/electrolyte interface, so as to form the base special type space charge layer that disappears, make electricity
Interface between pole/solid electrolyte forms the high impedance to lithium ion movement, causes battery to have higher DC internal resistance
With poor cycle performance.And solid polyelectrolyte, conventional forms as passed through lithium salts and linear polyether complexing
Thin film, although possess electrochemistry and chemical stability height and be easy to the feature for solidifying, but as polymer is formed with lithium salts
Solid polymer electrolyte in room temperature with higher crystalline phase, also result in battery with higher DC internal resistance and compared with
Difference cycle performance.
Therefore, for the research of all-solid lithium-ion battery, especially to reduce DC internal resistance, improve ionic conductivity and
The research for improving cycle performance has become urgent problem.
The content of the invention
The technical problem to be solved is to provide a kind of with low DC internal resistance, higher ionic conductivity and good
The all-solid lithium-ion battery of good cycle performance.
For reaching above-mentioned purpose, the invention provides a kind of manufacture method of all-solid lithium-ion battery, the manufacture method
Comprise the steps：
Step one：Polymer dielectric is dissolved in into N-Methyl pyrrolidone (NMP) solvent and makes glue；
Step 2：Positive pole main material, conductive agent are coated on positive collector after being sufficiently mixed with the glue obtained by step one,
Heated rear co-curing, obtains positive plate；Negative pole main material, conductive agent are coated on after being sufficiently mixed with the glue obtained by step one
On negative collector, heated rear co-curing obtains negative pole volume；
Step 3：To carry out under sulfide electrolyte room temperature after mechanical ball milling, be dissolved in nmp solvent and make slurry, be coated on
Negative pole rolls up surface, forms sulfide dielectric substrate, and heated solidify afterwards obtain negative plate；
Step 4：All-solid lithium-ion battery is obtained using the described positive plate of lamination process assembling and negative plate.
Preferably, in step one, polymer dielectric is polyethylene glycol oxide (PEO) system, polymethyl methacrylate
(PMMA) one or more in system, polyacrylonitrile (PAN) system, Kynoar (PVDF) system, polrvinyl chloride (PVC) system etc..
As polymer dielectric possesses adhesive property in itself, therefore without the need for additionally adding binding agent.During glue, polymer dielectric
Mass percent be 10～30%.
Preferably, in step 2, positive pole main material includes LiFePO4, cobalt acid lithium, lithium nickelate, LiMn2O4, nickel cobalt manganese three
One or more in first material etc., negative pole main material include the one kind in native graphite, Delanium, hard carbon, silica-base material etc.
Or it is several, conductive agent includes conductive carbon black (Super-P), electrically conductive graphite (KS-6), acetylene black, Graphene, CNT, gas phase
One or more in grown carbon fiber etc..
Preferably, in step 2, in positive pole pulping process, each component mass percent is：Positive pole main material 60～80%,
Conductive agent 3～5%, the glue 20～40% obtained by step one.In negative pole pulping process, each component mass percent is：Negative pole master
Material 60～80%, conductive agent 3～5%, the glue 20～45% obtained by step one.The solidification temperature of polymer dielectric be 50～
150 DEG C, hardening time is 1～12h.
Preferably, in step 3, sulfide electrolyte can be Li2S-SiS2-Li3PO4(M=Si, P, Ge, B, A1, Ga,
) etc. In one or more in.Ball milling is carried out using planetary mechanical ball grinding machine, ball milling bead selects zirconium oxide or three oxidations two
Aluminum bead, rotational speed of ball-mill are 200～800rpm, and Ball-milling Time is 3～24h.Sulfide electrolyte after ball milling prepares plastic, sulfur
The mass percent of compound electrolyte is 5～30%.
Preferably, in step 3, solidification temperature is 70～170 DEG C, and hardening time is 60～300s.Sulfide electrolyte
Thickness in monolayer after the heated solidification of layer is 5～50 μm.
Present invention also offers the all-solid lithium-ion battery that a kind of manufacture method in accordance with the above makes, this is complete solid
State lithium ion battery is made up with positive plate lamination of negative plate, and described positive plate includes positive collector (such as aluminium foil) and positive pole is applied
Layer, positive pole coating include polymer dielectric, conductive agent and positive pole main material, the negative plate comprising negative collector (such as Copper Foil),
Negative pole coating and sulfide dielectric substrate, negative pole coating include polymer dielectric, conductive agent and negative pole main material, sulfide electrolysis
Matter layer is coated on negative pole coating surface.
Compared with prior art, all-solid lithium-ion battery provided by the present invention has relatively low D.C. resistance, higher
Ionic conductivity and good cycle performance.Polymer dielectric is sufficiently mixed with both positive and negative polarity main material, increased contact area,
Ionic conductivity can be improved；Polymer dielectric also serves the effect of binding agent simultaneously.Polymer dielectric is to positive pole main material
Doping and local coat, between the interface of positive pole lithium-oxygen key and the lithium-sulfide linkage of sulfide electrolyte formed intercept, can be one
Determine in degree, to reduce the impedance between interface, be able to play the effect of sulfide electrolyte high ionic conductivity.Sulfide electrolyte
Negative pole is directly coated on using coating method and rolls up two surfaces, battery core is made in the direct superposition of rear both positive and negative polarity pole piece to punching in flakes, can be big
Big Simplified flowsheet, improve production efficiency.
Description of the drawings
Fig. 1 is a kind of sectional view of all-solid lithium-ion battery of the present invention.
Specific embodiment
Below by way of specific embodiment, comparative example and accompanying drawing, the invention will be further described, and these embodiments are only used
In the explanation present invention, it is not limiting the scope of the invention.
Embodiment 1:
(1) glue：In mass ratio 1:9, PEO based polymer electrolyte is dissolved in into nmp solvent, 3h is stirred at 20 DEG C and is configured to
Glue.
(2) positive pole slurrying：LiFePO4, Super-P and KS-6 are stirred and previous step using double-planet at 20 DEG C
Glue be sufficiently mixed 4h.Each component mass percent is：LiFePO4 70%, Super-P 3%, KS-6 3%, glue
24%.
(3) negative pole slurrying：Delanium and Super-P are stirred into the glue with previous step using double-planet at 20 DEG C
It is sufficiently mixed 4h.Each component mass percent is：Delanium 65%, Super-P 5%, glue 30%.
(4) polymer dielectric solidification：After both positive and negative polarity coating, at 90 DEG C of polymer dielectric, solidify 8h.
(5) sulfide electrolyte coating：Using planetary mechanical ball grinding machine by Li2S-SiS2-Li3PO4Ball milling 20h, rotating speed
For 600rpm.By the Li after ball milling2S-SiS2-Li3PO4With nmp solvent using double-planet stirring in mass ratio 1:4 prepare plastic
Liquid, is coated on negative pole and rolls up two surfaces, 150 DEG C of bakings 120s, the Li after solidification2S-SiS2-Li3PO4Thickness in monolayer is controlled in 35 μ
m。
(6) lamination：Both positive and negative polarity volume makes positive/negative plate Jing after punching, and Jing laminations make 10AH battery cores, using conventional method
Assemble the battery core all-solid lithium-ion battery is obtained with protection board, shell.
Embodiment 2:
(1) glue：In mass ratio 1:10, PMMA based polymer electrolyte is dissolved in into nmp solvent, 3h is stirred at 20 DEG C and is prepared
Into glue.
(2) positive pole slurrying：Cobalt acid lithium, Super-P and KS-6 are stirred and previous step using double-planet at 20 DEG C
Glue is sufficiently mixed 4h.Each component mass percent is：Cobalt acid lithium 70%, Super-P2.5%, KS-6 2.5%, glue
25%.
(3) negative pole slurrying：Delanium and gas-phase growth of carbon fibre are stirred and previous step using double-planet at 20 DEG C
Rapid glue is sufficiently mixed 4h.Each component mass percent is：Delanium 66%, gas-phase growth of carbon fibre 4%, glue
30%.
(4) polymer dielectric solidification：After both positive and negative polarity coating, at 80 DEG C of polymer dielectric, solidify 10h.
(5) sulfide electrolyte coating：Using planetary mechanical ball grinding machine by Li2S-SiS2-Li3GeO4Ball milling 22h, turns
Speed is 500rpm.By the Li after ball milling2S-SiS2-Li3GeO4With nmp solvent using double-planet stirring in mass ratio 1:4 are configured to
Glue, is coated on negative pole and rolls up two surfaces, 150 DEG C of bakings 180s, the Li after solidification2S-SiS2-Li3GeO4Thickness in monolayer control exists
30μm。
(6) lamination：Both positive and negative polarity volume makes positive/negative plate Jing after punching, and Jing laminations make 10AH battery cores, using conventional method
Assemble the battery core all-solid lithium-ion battery is obtained with protection board, shell.
Embodiment 3:
(1) glue：In mass ratio 1:9, PVDF based polymer electrolyte is dissolved in into nmp solvent, 3h is stirred at 20 DEG C and is prepared
Into glue.
(2) positive pole slurrying：LiMn2O4, Super-P and KS-6 are stirred and previous step using double-planet at 20 DEG C
Glue is sufficiently mixed 3.5h.Each component mass percent is：LiMn2O4 70%, Super-P2.5%, KS-6 2.5%, glue
25%.
(3) negative pole slurrying：Hard carbon, Graphene and Super-P are at 20 DEG C using double-planet stirring and the glue of previous step
Liquid is sufficiently mixed 3.5h.Each component mass percent is：Hard carbon 60%, Graphene 2%, Super-P 3%, glue 35%.
(4) polymer dielectric solidification：After both positive and negative polarity coating, at 85 DEG C of polymer dielectric, solidify 8h.
(5) sulfide electrolyte coating：Using planetary mechanical ball grinding machine by Li2S-SiS2-Li3BO4Ball milling 18h, rotating speed
For 550rpm.By the Li after ball milling2S-SiS2-Li3BO4With nmp solvent using double-planet stirring in mass ratio 1:5 prepare plastic
Liquid, is coated on negative pole and rolls up two surfaces, 140 DEG C of bakings 240s, the Li after solidification2S-SiS2-Li3BO4Thickness in monolayer is controlled in 30 μ
m。
(6) both positive and negative polarity volume makes positive/negative plate Jing after punching, and Jing laminations make 10AH battery cores, should using conventional method assembling
Battery core obtains all-solid lithium-ion battery with protection board, shell.
Embodiment 4:
(1) glue：In mass ratio 1:9, PAN based polymer electrolyte is dissolved in into nmp solvent, 3h is stirred at 20 DEG C and is configured to
Glue.
(2) positive pole slurrying：Nickel-cobalt-manganese ternary material, Super-P and KS-6 are stirred with using double-planet at 20 DEG C
The glue of one step is sufficiently mixed 4h.Each component mass percent is：Nickel-cobalt-manganese ternary material 70%, Super-P 2.5%,
KS-6 2.5%, glue 25%.
(3) negative pole slurrying：Si-C composite material and Graphene are stirred and previous step using double-planet at 20 DEG C
Glue is sufficiently mixed 4h.Each component mass percent is：Si-C composite material 62%, Graphene 3%, glue 35%.
(4) polymer dielectric solidification：After both positive and negative polarity coating, at 90 DEG C of polymer dielectric, solidify 10h.
(5) sulfide electrolyte coating：Using planetary mechanical ball grinding machine by Li2S-SiS2-Li3AlO4Ball milling 18h, turns
Speed is 500rpm.By the Li after ball milling2S-SiS2-Li3AlO4With nmp solvent using double-planet stirring in mass ratio 1:5 are configured to
Glue, is coated on negative pole and rolls up two surfaces, 110 DEG C of bakings 240s, the Li after solidification2S-SiS2-Li3AlO4Thickness in monolayer control exists
35μm。
(6) both positive and negative polarity volume makes positive/negative plate Jing after punching, and Jing laminations make 10AH battery cores, should using conventional method assembling
Battery core obtains all-solid lithium-ion battery with protection board, shell.
Embodiment 5:
(1) glue：In mass ratio 1:11, PVC based polymer electrolyte is dissolved in into nmp solvent, 3h is stirred at 20 DEG C and is prepared
Into glue.
(2) positive pole slurrying：By LiFePO4, nickel-cobalt-manganese ternary material, Super-P and KS-6 at 20 DEG C adopt double-planet
Stirring is sufficiently mixed 5h with the glue of previous step.Each component mass percent is：LiFePO4 35%, nickel-cobalt-manganese ternary material
35%th, Super-P 2.5%, KS-6 2.5%, glue 25%.
(3) negative pole slurrying：By Si-C composite material, gas-phase growth of carbon fibre and Super-P at 20 DEG C adopt double-planet
Stirring is sufficiently mixed 5h with the glue of previous step.Each component mass percent is：Si-C composite material 65%, vapor grown carbon
Fiber 2%, Super-P 3%, glue 30%.
(4) polymer dielectric solidification：After both positive and negative polarity coating, at 90 DEG C of polymer dielectric, solidify 10h.
(5) sulfide electrolyte coating：Using planetary mechanical ball grinding machine by Li2S-SiS2-Li3InO4Ball milling 20h, turns
Speed is 750rpm.By the Li after ball milling2S-SiS2-Li3InO4With nmp solvent using double-planet stirring in mass ratio 1:5 are configured to
Glue, is coated on negative pole and rolls up two surfaces, 130 DEG C of bakings 180s, the Li after solidification2S-SiS2-Li3InO4Thickness in monolayer control exists
30μm。
(6) both positive and negative polarity volume makes positive/negative plate Jing after punching, and Jing laminations make 10AH battery cores, should using conventional method assembling
Battery core obtains all-solid lithium-ion battery with protection board, shell.
As shown in figure 1, a kind of sectional view of the all-solid lithium-ion battery made for the present invention, all solid state lithium ion electricity
Pond is made up with positive plate lamination of negative plate, and described positive plate includes positive collector 1 (such as aluminium foil) and positive pole coating, and positive pole is applied
Layer includes polymer dielectric 3, conductive agent and positive pole main material 2, and the negative plate is applied comprising negative collector 6 (such as Copper Foil), negative pole
Layer and sulfide dielectric substrate 4, negative pole coating include polymer dielectric 3, conductive agent and negative pole main material 5, sulfide electrolyte
Layer 4 is coated on negative pole coating surface.
Comparative example 1：
(1) positive pole slurrying：By nickel-cobalt-manganese ternary material, Super-P, KS-6, PVDF and NMP at 20 DEG C adopt double-planet
Stirring is sufficiently mixed 4h.Each component mass percent is：Nickel-cobalt-manganese ternary material 66.5%, Super-P1.4%, KS-6
0.7%th, PVDF1.4%, NMP30%.
(2) negative pole slurrying：Si-C composite material, Graphene, PVDF and NMP is abundant using double-planet stirring at 20 DEG C
Mixing 4h.Each component mass percent is：Si-C composite material 55.8%, Graphene 1.8%, PVDF2.4%, NMP40%.
(3) lamination：Both positive and negative polarity is coated, make positive/negative plate after punching, by positive/negative plate and solid sulfide barrier film Jing
Lamination makes 10AH battery cores, assembles the battery core using conventional method and obtains solid lithium ion battery with protection board, shell.
Comparative example 2：
(1) glue：In mass ratio 1:9, PAN based polymer electrolyte is dissolved in into nmp solvent, 3h is stirred at 20 DEG C and is configured to
Glue.
(2) positive pole slurrying：Nickel-cobalt-manganese ternary material, Super-P and KS-6 are stirred with using double-planet at 20 DEG C
The glue of one step is sufficiently mixed 4h.Each component mass percent is：Nickel-cobalt-manganese ternary material 70%, Super-P 2.5%,
KS-6 2.5%, glue 25%.
(3) negative pole slurrying：Si-C composite material and Graphene are stirred and previous step using double-planet at 20 DEG C
Glue is sufficiently mixed 4h.Each component mass percent is：Si-C composite material 62%, Graphene 3%, glue 35%.
(4) polymer dielectric solidification：After both positive and negative polarity coating, at 90 DEG C of polymer dielectric, solidify 10h.
(5) lamination：Both positive and negative polarity volume makes positive/negative plate Jing after punching, by positive/negative plate and solid sulfide barrier film Jing laminations
10AH battery cores are made, and the battery core is assembled using conventional method and solid lithium ion battery is obtained with protection board, shell.
Comparative example 3：
(1) positive pole slurrying：By nickel-cobalt-manganese ternary material, Super-P, KS-6, PVDF and NMP at 20 DEG C adopt double-planet
Stirring is sufficiently mixed 4h.Each component mass percent is：Nickel-cobalt-manganese ternary material 66.5%, Super-P1.4%, KS-6
0.7%th, PVDF1.4%, NMP30%.
(2) negative pole slurrying：By Si-C composite material, Graphene, PVDF and NMP are abundant using double-planet stirring at 20 DEG C
Mixing 4h.Each component mass percent is：Si-C composite material 55.8%, Graphene 1.8%, PVDF2.4%, NMP40%.
(3) sulfide electrolyte coating：Using planetary mechanical ball grinding machine by Li2S-SiS2-Li3InO4Ball milling 20h, turns
Speed is 750rpm.By the Li after ball milling2S-SiS2-Li3InO4With nmp solvent using double-planet stirring in mass ratio 1:5 are configured to
Glue, is coated on negative pole and rolls up two surfaces, 130 DEG C of bakings 180s, the Li after solidification2S-SiS2-Li3InO4Thickness in monolayer control exists
30μm。
(4) lamination：Both positive and negative polarity volume makes positive/negative plate Jing after punching, and Jing laminations make 10AH battery cores, using conventional method
Assemble the battery core solid lithium ion battery is obtained with protection board, shell.
The solid lithium ion battery that embodiment 1～5 and comparative example 1～3 are made by the following method test loop performance and
DC internal resistance.
Cycle performance：At 25 DEG C of room temperature, by battery 1C constant-current charges to 4.2V, then constant-voltage charge, cut-off current is
0.05C；Subsequently by battery 1C multiplying powers constant-current discharge to 2.75V, the initial discharge capacity C of battery is obtained0, then according to above-mentioned fill
Discharge system carries out charge and discharge cycles to battery, and the capacitance for obtaining battery is Cd, according to L=Cd/C0× 100% method meter
Calculate the discharge capacitance of battery after circulating.
DC internal resistance：Under room temperature, battery shelves 60min with 1C constant-current discharges to 2.755V；Battery is filled with 1C constant current constant voltages
Electricity shelves 60min to 4.2V, constant-voltage charge to electric current≤0.05C cut-offs；1C constant-current discharge 30min；Shelve 60min；1C constant currents
Electric discharge 10s, lower voltage limit 2.5V.Open-circuit voltage in recording impulse discharge process, and calculate DC internal resistance.
DC internal resistance computing formula (is calculated using 1C-HPPC open-circuit voltages)
The solid lithium ion battery that embodiment 1～5 and comparative example 1～3 make is circulated performance and DC internal resistance test
Result be summarized in table 1.
The test result of 1 above-described embodiment of table and comparative example cycle performance and DC internal resistance
| Sequence number | 500 capability retention/% of circulation | DC internal resistance/m Ω |
| Embodiment 1 | 95.6 | 3.09 |
| Embodiment 2 | 95.2 | 3.02 |
| Embodiment 3 | 94.7 | 3.11 |
| Embodiment 4 | 95.1 | 2.98 |
| Embodiment 5 | 94.5 | 3.06 |
| Comparative example 1 | 90.5 | 5.68 |
| Comparative example 2 | 92.7 | 4.37 |
| Comparative example 3 | 92.3 | 4.25 |
In terms of the DC internal resistance of battery, from the test result of comparative example 1 in table 1, using conventional scheme preparation
Into solid lithium ion battery, DC internal resistance is higher.And knowable to the result of comparative example 2 and 3, add in both positive and negative polarity main material poly-
Sulfide electrolyte is directly coated on negative plate surface by polymer electrolyte, can reduce the DC internal resistance of battery.This is
Because polymer dielectric is sufficiently mixed with both positive and negative polarity main material, contact area is increased, ionic conductivity can be improved；Vulcanize simultaneously
Thing electrolyte is directly coated on two surface of negative plate using coating method, can reduce the impedance between interface to a certain extent.Compare
In comparative example 1～3, the embodiment of the present invention 1～5 adds polymer dielectric and will vulcanize in passing through to adopt both positive and negative polarity main material simultaneously
The method that thing electrolyte is directly coated on negative plate surface, hence it is evident that reduce the DC internal resistance of battery.
In terms of the cycle performance of battery, from the test result of comparative example 1 in table 1, using conventional scheme preparation
Into solid lithium ion battery cycle performance it is worst.And knowable to the result of comparative example 2 and 3, add in both positive and negative polarity main material poly-
Sulfide electrolyte is directly coated on negative plate surface by polymer electrolyte, can improve the cycle performance of battery.Compare
In comparative example 1～3, while using adding polymer dielectric in both positive and negative polarity main material and be directly coated on sulfide electrolyte negative
The cycle performance of battery of the embodiment 1～5 of pole piece is significantly improved.
It is although present disclosure has been made to be discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
Various modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of manufacture method of all-solid lithium-ion battery, it is characterised in that the manufacture method comprises the steps：
Step one：Polymer dielectric is dissolved in into solvent and makes glue；
Step 2：Positive pole main material, conductive agent are coated on positive collector after being sufficiently mixed with the glue obtained by step one, Jing adds
Co-curing after heat, obtains positive plate；Negative pole main material, conductive agent are coated on into negative collection after being sufficiently mixed with the glue obtained by step one
On fluid, heated rear co-curing obtains negative pole volume；
Step 3：Sulfide electrolyte is carried out, after mechanical ball milling, being dissolved in solvent and making slurry, negative pole volume surface, shape is coated on
Sulphidisation dielectric substrate, heated solidify afterwards, obtains negative plate；
Step 4：All-solid lithium-ion battery is obtained using the described positive plate of lamination process assembling and negative plate.
2. the manufacture method of all-solid lithium-ion battery according to claim 1, it is characterised in that in step one, gathers
Polymer electrolyte is PEO systems, PMMA systems, PAN systems, PVDF systems, one or more in PVC systems.
3. the manufacture method of all-solid lithium-ion battery according to claim 1, it is characterised in that in step one, institute
In the glue stated, the mass percent of polymer dielectric is 10～30%.
4. the manufacture method of all-solid lithium-ion battery according to claim 1, it is characterised in that in step 2, institute
The positive pole main material stated is LiFePO4, cobalt acid lithium, lithium nickelate, LiMn2O4, one or more in nickel-cobalt-manganese ternary material；It is described
Negative pole main material be native graphite, Delanium, hard carbon, one or more in silica-base material；Described conductive agent is
One or more in Super-P, KS-6, acetylene black, Graphene, CNT, gas-phase growth of carbon fibre.
5. the manufacture method of all-solid lithium-ion battery according to claim 1, it is characterised in that in step 2, just
In the pulping process of pole, each component mass percent is：Positive pole main material 60～80%, conductive agent 3～5%, the glue obtained by step one
15～37%；In negative pole pulping process, each component mass percent is：Negative pole main material 60～80%, conductive agent 3～5%, step
Glue 15～37% obtained by one.
6. the manufacture method of all-solid lithium-ion battery according to claim 1, it is characterised in that in step 2, Gu
It is 50～150 DEG C to change temperature, and hardening time is 1～12h；In step 3, solidification temperature is 70～170 DEG C, and hardening time is
60～300s.
7. the manufacture method of all-solid lithium-ion battery according to claim 1, it is characterised in that in step 3, institute
The sulfide electrolyte stated can be Li2S-SiS2-Li3MO4In one or more, wherein M=Si, P, Ge, B, A1, Ga, In.
8. the manufacture method of all-solid lithium-ion battery according to claim 1, it is characterised in that in step 3, ball
The ball milling bead used by grinding process is zirconium oxide or aluminium sesquioxide bead, and rotational speed of ball-mill is 200～800rpm, Ball-milling Time
For 3～24h.
9. the manufacture method of all-solid lithium-ion battery according to claim 1, it is characterised in that in step 3, sulfur
The mass percent of compound electrolyte is 5～30%.
10. the all-solid lithium-ion battery that a kind of manufacture method according to claim 1-9 any one makes, including just
Pole piece and negative plate, it is characterised in that the positive plate includes positive collector (1) and positive pole coating, positive pole coating includes polymerization
Thing electrolyte (3), conductive agent and positive pole main material (2), the negative plate include negative collector (6), negative pole coating and sulfide electricity
Solution matter layer (4), negative pole coating include polymer dielectric (3), conductive agent and negative pole main material (5), and sulfide dielectric substrate (4) is applied
It is overlying on negative pole coating surface.
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