CN108550835A - A kind of LiFePO4/gel electrolyte composite positive pole and preparation method thereof and a kind of solid state lithium battery and preparation method thereof - Google Patents
A kind of LiFePO4/gel electrolyte composite positive pole and preparation method thereof and a kind of solid state lithium battery and preparation method thereof Download PDFInfo
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- CN108550835A CN108550835A CN201810558684.5A CN201810558684A CN108550835A CN 108550835 A CN108550835 A CN 108550835A CN 201810558684 A CN201810558684 A CN 201810558684A CN 108550835 A CN108550835 A CN 108550835A
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- Prior art keywords
- lithium
- electrolyte
- anode
- lifepo4
- lifepo
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 101
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 70
- 239000007787 solid Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims abstract description 79
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 72
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 61
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims abstract description 59
- 239000012266 salt solution Substances 0.000 claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 238000007711 solidification Methods 0.000 claims abstract description 27
- 230000008023 solidification Effects 0.000 claims abstract description 27
- 239000002202 Polyethylene glycol Substances 0.000 claims description 42
- 229920001223 polyethylene glycol Polymers 0.000 claims description 42
- 125000004386 diacrylate group Chemical group 0.000 claims description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 36
- 239000008151 electrolyte solution Substances 0.000 claims description 33
- 239000001913 cellulose Substances 0.000 claims description 27
- 229920002678 cellulose Polymers 0.000 claims description 27
- 239000012528 membrane Substances 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000011149 active material Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- -1 conductive black Substances 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 5
- 239000004425 Makrolon Substances 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract 1
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 31
- 238000000034 method Methods 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- UFLFSNVZQRNKOX-UHFFFAOYSA-N carbonic acid;ethenyl acetate Chemical compound OC(O)=O.CC(=O)OC=C UFLFSNVZQRNKOX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of LiFePO4/gel electrolyte composite positive poles and preparation method thereof.The present invention is during preparing composite positive pole, LiFePO 4 powder and conductive black and lithium salt solution etc. are coated in the form of homogeneous slurry and carry out ultraviolet light solidification again on a current collector, so that electrolyte is uniformly coated on lithium iron phosphate nano particle surface, it realizes LiFePO 4 powder surface and uniformly coats gel electrolyte, realize the combination of positive electrode and electrolyte molecule rank, to significantly increase the contact area between electrolyte and LiFePO4, the transfer and transmission for promoting lithium ion, reduce polarization of electrode and interface impedance.The present invention also provides a kind of using the solid state lithium battery that anode obtains described in above-mentioned technical proposal.
Description
Technical field
The invention belongs to solid state lithium battery technical field more particularly to a kind of LiFePO4/gel electrolyte anode composites
Material and preparation method thereof and a kind of solid state lithium battery and preparation method thereof.
Background technology
With the continuous development of global economy, the continuous improvement of living standards of the people, energy and environmental problem is also increasingly prominent
Go out.As the carrier of electric energy storage, lithium rechargeable battery has that energy density is high, have extended cycle life, self discharge effect is small, right
The advantages such as environmental-friendly have been widely used in the fields such as mobile phone, digital portable product at present.Electrolyte is as lithium ion
Important component in battery, in the important function for playing transmission ion.However, conventional lithium ion battery electrolyte is let out
The safety problems such as dew, burning even explosion frequently occurred in recent years, became a kind of potential security risk.
Solid electrolyte compare with conventional liquid electrolyte, have it is nonflammable, not volatile, without leakage etc. advantages, can
Fundamentally solve the safety issue of lithium ion battery；Meanwhile solid electrolyte has broader potential window, and can be with
Replace electrolyte and diaphragm simultaneously, the operating voltage of battery can be significantly improved, improve the energy density of battery；In addition, solid-state
Electrolyte also has higher thermal stability and mechanical strength, thus theoretically can make battery under more harsh environmental condition
It works and there is longer cycle life；The above-mentioned advantage of solid electrolyte so that solid state lithium battery is concerned.
However, it is the interface between solid state electrode and solid electrolyte to hinder the main bottleneck of solid electrolyte application at present
Problem, transfer of the lithium ion between electrode and electrolyte is hindered, seriously affects high rate capability, the stable circulation of battery
Property etc..
Invention content
In view of this, the present invention provides a kind of LiFePO4/gel electrolyte composite positive poles and preparation method thereof
With a kind of solid state lithium battery and preparation method thereof, LiFePO4 prepared by the present invention/gel electrolyte composite positive pole and electricity
Contact is good between solving matter, excellent with the lithium battery cyclical stability that this is obtained.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of LiFePO4/gel electrolyte composite positive pole, including collector and in the collection
The active material composite of flow surface；
The active material composite includes LiFePO 4 powder, conductive black and is wrapped in LiFePO 4 powder and leads
The gel electrolyte of electric carbon blacksurface；
The gel electrolyte contains the polyethyleneglycol diacrylate and solidification lithium salts electrolyte of polymerization.
Preferably, the mass ratio of the LiFePO 4 powder and conductive black is preferably (3~4):1；
In the solidification lithium salts electrolyte in elemental lithium and the polyethyleneglycol diacrylate of polymerization-CCO- segments mole
Than for (7~9)：1；
The mass ratio of lithium salts and LiFePO 4 powder is 1 in the solidification lithium salts electrolyte:(8~70)；
The active material composite is 0.6~1.8g/cm in the covering amount of collection liquid surface2。
The present invention also provides a kind of preparation method of LiFePO4/gel electrolyte composite positive pole, including it is following
Step：
(1) by LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate, photoinitiator, lithium salt solution and dispersion
Solvent mixing homogeneous, obtains homogeneous slurry；
(2) the homogeneous slurry in the step (1) is coated in collection liquid surface, obtains pole piece；
(3) pole piece for obtaining the step (2) carries out ultraviolet light solidification, and it is compound to obtain LiFePO4/gel electrolyte
Positive electrode.
Preferably, the grain size of the LiFePO 4 powder is 200~800nm；
The relative molecular mass of the polyethyleneglycol diacrylate is 400~1000；
The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone；
The dispersion solvent is anhydrous acetonitrile.
Preferably, the mass ratio of the LiFePO 4 powder and conductive black is (3~4):1；
The molar ratio of lithium ion and-CCO- segments in polyethyleneglycol diacrylate is (7~9) in the lithium salt solution：
1；
The mass ratio of lithium salts and LiFePO 4 powder is 1 in the lithium salt solution:(8~70)；
The quality of the photoinitiator is the 1%~5% of polyethyleneglycol diacrylate quality；
The volume of the dispersion solvent and the mass ratio of LiFePO 4 powder are (0.8~2) mL：1g.
Preferably, lithium salts is LiTFSI, LiClO in the lithium salt solution4And LiPF6In it is one or more；
Solvent includes ethylene carbonate and secondary solvent in the lithium salt solution, the secondary solvent be diethyl carbonate,
It is one or more in dimethyl carbonate and makrolon.
Preferably, the coated weight coated in the step (2) is with LiFePO 4 powder in homogeneous slurry, conductive black, poly-
The gross mass meter of glycol diacrylate, photoinitiator and lithium salt solution is 0.6~1.8g/cm2。
The present invention provides a kind of solid state lithium batteries, including anode, cellulose membrane and the lithium anode set gradually, institute
The material for stating anode is the LiFePO4/gel electrolyte composite positive pole or above-mentioned technical proposal described in above-mentioned technical proposal
The LiFePO4 that the preparation method is prepared/gel electrolyte composite positive pole；
Contain electrolyte between the anode and lithium anode, the electrolyte be include polyethylene glycol diacrylate
The solidfied material of the electrolyte solution of ester, initiator and lithium salt solution.
The present invention also provides the preparation methods of the solid state lithium battery described in above-mentioned technical proposal, include the following steps：
(I) LiFePO4 described in techniques described above scheme/gel electrolyte composite positive pole or above-mentioned technical proposal
The LiFePO4 that the preparation method is prepared/gel electrolyte composite positive pole is as anode, using lithium metal as bearing
The anode, cellulose membrane and lithium anode are set gradually, obtain cell matrix by pole；
(II) it after injecting the electrolyte solution between the anode and lithium anode of the cell matrix, is packaged
Obtain button cell；The electrolyte solution includes polyethyleneglycol diacrylate, initiator and lithium salt solution；
(III) button cell that the step (II) obtains is heated, obtains solid state lithium battery.
Preferably, the temperature heated in the step (III) is 60~70 DEG C, and the time of heat treatment is 2~6h.
The present invention provides a kind of LiFePO4/gel electrolyte composite positive pole, including collector and in the collection
The active material composite of flow surface；The active material composite includes LiFePO 4 powder, conductive black and is wrapped in
The gel electrolyte of LiFePO 4 powder and conductive black surface, and gel electrolyte contains the polyethylene glycol diacrylate of polymerization
Ester and solidification lithium salts electrolyte.LiFePO4 provided by the invention/gel electrolyte anode composite realizes electrolyte equably
Be coated on lithium iron phosphate nano particle surface, the contact area to both significantly increase, promote lithium ion transfer and
Transmission, reduces polarization of electrode and interface impedance.
The present invention also provides a kind of preparation method of LiFePO4/gel electrolyte composite positive pole, the present invention exists
During preparing composite positive pole, by LiFePO 4 powder and conductive black and lithium salt solution etc. in the form of homogeneous slurry
Coating carries out ultraviolet light solidification again on a current collector so that electrolyte is uniformly coated on lithium iron phosphate nano particle surface, real
Show LiFePO 4 powder surface and uniformly coated gel electrolyte, realizes the knot of positive electrode and electrolyte molecule rank
It closes, significantly increases the contact area between electrolyte and LiFePO4, promote the transfer and transmission of lithium ion, reduce electricity
The polarization of pole and interface impedance avoid solid electrolyte mobility bad, it is difficult to penetrate into the biography resulted in the hole of anode
The problem of defeated effect difference.
Embodiment the result shows that, using LiFePO4/gel electrolyte composite positive pole for being prepared of the present invention
The solid state lithium battery high rate performance of preparation is excellent, still has 87.3% capacity to keep after solid lithium circulating battery 100 times, coulomb effect
Rate is maintained at 99.5% or more, shows good cyclical stability.
In addition, the present invention prepares solid state lithium battery by the method for in-situ solidifying, electrode is made closely to be connect with electrolyte layer
It touches, it is ensured that enough lithium ion transport channels can meet carry out charge and discharge of the battery under larger current density.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the different multiples SEM figures of LiFePO4/gel electrolyte anode composite prepared by embodiment 1；
Fig. 2 is the TEM figures for LiFePO4/gel electrolyte anode composite that embodiment 1 obtains.
Fig. 3 is LiFePO4/gel electrolyte anode composite and gel electrolyte in the solid state lithium battery that embodiment 1 obtains
The SEM at interface schemes；
Fig. 4 is the high rate performance figure for the solid state battery that embodiment 1 obtains；
Fig. 5 is cycle performance figure of the obtained solid state battery of embodiment 1 under 1C current densities；
Fig. 6 is electrochemical impedance collection of illustrative plates of the obtained solid state battery of embodiment 1 before cycle after numbers different with cycle.
Specific implementation mode
The present invention provides a kind of LiFePO4/gel electrolyte composite positive pole, including collector and in the collection
The active material composite of flow surface；
The active material composite includes LiFePO 4 powder, conductive black and is wrapped in LiFePO 4 powder and leads
The gel electrolyte of electric carbon blacksurface；
The gel electrolyte contains the polyethyleneglycol diacrylate and solidification lithium salts electrolyte of polymerization.
LiFePO4 provided by the invention/gel electrolyte composite positive pole includes collector and in collection liquid surface
Active material composite.In the present invention, the collector is preferably aluminium flake collector；The present invention is to the aluminium flake collector
Size does not have particular/special requirement, using well-known to those skilled in the art.
In the present invention, the active material composite is evenly coated at collection liquid surface；The active material composite
It is preferably 0.6~1.8g/cm in the covering amount of collection liquid surface2, further preferably 0.6~1.8g/cm2.In the present invention,
The active material composite includes LiFePO 4 powder, conductive black and is wrapped in LiFePO 4 powder and conductive black table
The gel electrolyte in face.In the present invention, the grain size of the LiFePO 4 powder is preferably 200~800nm, further preferably
400~600nm.The present invention uses the LiFePO 4 powder of the grain size, can shorten the path of ion and electron-transport, improves
Transmission speed, and then improve the high rate performance of anode.
In the present invention, the mass ratio of the LiFePO 4 powder and conductive black is preferably (3~4):1, it is further excellent
It is selected as (3.5~3.8)：1.The present invention does not have particular/special requirement to the source of the LiFePO 4 powder and conductive black, using this
Known to field technology personnel.
In the present invention, the gel electrolyte is wrapped in LiFePO 4 powder surface and conductive black surface.In this hair
In bright, the gel electrolyte contains the polyethyleneglycol diacrylate and solidification lithium salts electrolyte of polymerization；The gel electrolyte
Matter carries after being cured using lithium salt solution by molecular skeleton of gel-forming using the polyethyleneglycol diacrylate polymerizeing as molecular skeleton
For decentralized medium.
In the present invention, the solidification lithium salts electrolyte, that is, lithium salt solution directly cures obtained spawn.At this
In invention, for curing, solvent in the lithium salt solution for obtaining curing lithium salts electrolyte preferably includes ethylene carbonate and auxiliary is molten
Agent, the secondary solvent are further one or more in diethyl carbonate, dimethyl carbonate and makrolon；The carbonic acid
Vinyl acetate and the volume ratio of secondary solvent are preferably 1:1.The present invention does not have particular/special requirement to the source of the lithium salts and solvent, adopts
With well-known to those skilled in the art.In the present invention, the molar concentration of lithium ion is preferably in the lithium salt solution
1mol/L；The solvent hardly happens volatilization in the curing process, is fully retained in gel electrolyte.In the present invention,
Lithium salts is preferably LiTFSI, LiClO in the solidification lithium salts electrolyte4And LiPF6In it is one or more.In the present invention, institute
The molar ratio for stating-CCO- segments in elemental lithium and the polyethyleneglycol diacrylate of polymerization in solidification lithium salts electrolyte is preferably (7
~9)：1, further preferably 8:1；The mass ratio of lithium salts and LiFePO 4 powder is preferably 1 in the solidification lithium salts electrolyte:
(8~70), further preferably 1：(20~30).
The present invention provides a kind of preparation methods of LiFePO4/gel electrolyte composite positive pole, including following step
Suddenly：
(1) by LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate, photoinitiator, lithium salt solution and dispersion
Solvent mixing homogeneous, obtains homogeneous slurry；
(2) the homogeneous slurry that the step (1) is prepared is coated in collection liquid surface, obtains pole piece；
(3) pole piece for obtaining the step (2) carries out ultraviolet light solidification, and it is compound to obtain LiFePO4/gel electrolyte
Positive electrode.
The present invention by LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate, photoinitiator, lithium salt solution and
Dispersion solvent mixes homogeneous, obtains homogeneous slurry.
In the present invention, the mass ratio of the LiFePO 4 powder and conductive black is preferably (3~4):1, it is further excellent
It is selected as (3.2~3.5)：1.In the present invention, the LiFePO 4 powder and conductive black with it is compound described in preceding solution
Consistent in material, details are not described herein.
In the present invention, lithium salts is preferably LiTFSI, LiClO in the lithium salt solution4And LiPF6In it is one or more.
In the present invention, solvent preferably includes ethylene carbonate and secondary solvent in the lithium salt solution, and the secondary solvent is further
It is one or more in diethyl carbonate, dimethyl carbonate and makrolon；The body of the ethylene carbonate and secondary solvent
Product is than preferably 1:1.The present invention does not have particular/special requirement to the source of the lithium salts and solvent, ripe using those skilled in the art institute
Know.In the present invention, the molar concentration of lithium ion is preferably 1mol/L in the lithium salt solution.In the present invention, institute
Lithium salt solution is stated as lithium-ion electrolyte.
In the present invention, the mass ratio of lithium salts and LiFePO 4 powder is preferably 1 in the lithium salt solution:(8~70), into
One step is preferably 1：(20~30).
In the present invention, the relative molecular mass of the polyethyleneglycol diacrylate (PEGDA) be preferably 400~
1000, further preferably 450~850, more preferably 500~600.In the present invention, the effect of the PEGDA is to provide friendship
The polymer network of connection promotes the solidification of the lithium salt solution in homogeneous slurry, meanwhile ,-EO- segments (i.e.-CCO- in the PEGDA
Segment) there are conducting lithium ions.
In the present invention, lithium ion and-CCO- segments in raw material polyethyleneglycol diacrylate in the lithium salt solution
Molar ratio is preferably (7~9)：1, further preferably (7.5~8)：1.
In the present invention, the photoinitiator is preferably 2- hydroxy-2-methyl -1- phenyl -1- acetone；The photoinitiator
Quality be preferably the 1%~5% of polyethyleneglycol diacrylate quality, further preferably 1.5%~3%.In the present invention
In, the effect of the photoinitiator is that the carbon-carbon double bond opening of PEGDA is triggered under the irradiation of ultraviolet light, causes the poly- of PEGDA
Conjunction obtains final gel electrolyte.
In the present invention, the dispersion solvent is preferably anhydrous acetonitrile；The volume of the dispersion solvent and LiFePO4 powder
The mass ratio of body is preferably (0.8~2) mL：1g, further preferably (0.9~1.2) mL：1g.In the present invention, the dispersion
Solvent plays the role of the positive raw material of dispersion, reduces slurry viscosity, is convenient for the coating of follow-up pole piece, due to acetonitrile high volatility,
It can quickly be vapored away during coating pole piece and ultra-violet curing.
The present invention is molten to the LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate, photoinitiator, lithium salts
The hybrid mode of liquid and dispersion solvent does not have particular/special requirement, is using feed liquid hybrid mode well-known to those skilled in the art
It can.In the present invention, the mixing specifically carries out under agitation.
After obtaining homogeneous slurry, the homogeneous slurry is coated in collection liquid surface by the present invention, obtains pole piece.In the present invention
In, the collector is consistent in aforementioned phosphate iron lithium/gel electrolyte composite positive pole technical solution, no longer superfluous herein
It states.In the present invention, the coated weight of the coating is with LiFePO 4 powder, conductive black, polyethylene glycol dipropyl in homogeneous slurry
The gross mass meter of olefin(e) acid ester, photoinitiator and lithium salt solution, preferably 0.6~1.8g/cm2, further preferably 0.8~
1.6g/cm2, more preferably 1.0~1.2g/cm2.The present invention does not have particular/special requirement to the specific implementation mode of the coating, uses
Mode well-known to those skilled in the art in collection liquid surface coating slurry.
After coating, the pole piece is carried out ultraviolet light solidification by the present invention, obtains LiFePO4/gel electrolyte anode composite
Material.In the present invention, the ultraviolet light cured time is preferably 10~30min, further preferably 15~28min, more
Preferably 20~25min.In the present invention, pole piece is carried out solidification process by the ultraviolet light solidification under ultraviolet light.
In the present invention, the ultraviolet light solidification occurs PEGDA and polymerisation all occurs, and obtains cross-linked network, realizes that electrode is complete
Solidification.
The volatilization of dispersion solvent occurs during ultraviolet light solidification for the present invention, while under the excitation of ultraviolet light,
Sudden reaction is opened and occurred to the double bond of photoinitiator triggering PEGDA, forms the polymer backbone of gel electrolyte；Lithium salt solution
In solvent property stablize, it is not volatile, in the curing process, remain in collection liquid surface, lithium-ion electrolyte is polymerizeing
It is formed by curing gel electrolyte in object skeleton, is uniformly coated on lithium iron phosphate nano particle surface, while being coated on conductive charcoal
Black surface realizes LiFePO 4 powder surface and uniformly coats gel electrolyte, realizes positive electrode and electrolyte molecule
The combination of rank, to significantly increase the contact area between electrolyte and LiFePO4, promote lithium ion transfer and
Transmission, reduces polarization of electrode and interface impedance.
In the present invention, the ultra-violet curing obtains including collector and the LiFePO4 powder coated in collection liquid surface
Body, conductive black and the gel electrolyte for being wrapped in LiFePO 4 powder and conductive black surface；The gel electrolyte contains
There are the polyethyleneglycol diacrylate of polymerization and cured lithium salt solution.In the present invention, the photoinitiator levels are less, can
It ignores.
In the present invention, the preparation of the LiFePO4/gel electrolyte composite positive pole is preferably under protection of argon gas
It carries out；The embodiment of the present invention specifically carries out in the glove box full of argon gas.
In the present invention, the LiFePO4/gel electrolyte composite positive pole is used as solid state lithium battery anode；
After the ultraviolet light solidification, the present invention preferably cuts curing materials, obtains the solid state lithium battery anode of target size.
The present invention provides a kind of solid state lithium batteries, including anode, cellulose membrane and the lithium anode set gradually, institute
The material for stating anode is LiFePO4/gel electrolyte composite positive pole or the above-mentioned technical side described in above-mentioned technical proposal
The LiFePO4 that preparation method described in case is prepared/gel electrolyte composite positive pole；The anode and lithium anode
Between contain electrolyte, the electrolyte be include polyethyleneglycol diacrylate, initiator and lithium salt solution electrolyte it is molten
The solidfied material of liquid.
Solid state lithium battery provided by the invention includes the anode, cellulose membrane and lithium anode set gradually.In this hair
In bright, the material of the anode is LiFePO4/gel electrolyte composite positive pole described in above-mentioned technical proposal.In this hair
In bright, the cathode is preferably metal lithium sheet.The present invention does not have particular/special requirement to the size of the anode, cathode, using ability
Solid state lithium battery anode known to field technique personnel and lithium anode size.
In the present invention, the thickness of the cellulose membrane is preferably 30~40 μm；The density of the cellulose membrane is preferably
0.4~0.5g/cm3, the air drag of the cellulose membrane is preferably 80~150sec/100ml.The present invention is to the cellulose
The source of film does not have particular/special requirement, using commercial goods well-known to those skilled in the art.In the present invention, the fibre
The plain film of dimension plays the role of support electrolyte between anode and lithium anode, improves electrolyte strength；Also act as barrier
The effect of anode and lithium anode.
In the present invention, contain electrolyte between the anode and lithium anode；The electrolyte is located at cellulose membrane
In the hole of both sides and cellulose membrane, electrolyte and cellulose membrane collectively reside between anode and lithium anode.
The electrolyte is the solidification for the electrolyte solution for including polyethyleneglycol diacrylate, initiator and lithium salt solution
Object；The electrolyte is more preferably that the electrolyte solution cures 2~6h at 60~70 DEG C and obtains.In the present invention, institute
It is more preferably 65~68 DEG C to state cured temperature；The cured time is more preferably 3~5h.
In the present invention, the quality of polyethyleneglycol diacrylate is preferably that electrolyte solution is total in the electrolyte solution
The 5~20% of quality, further preferably 6~18%, more preferably 7~15%.
In the present invention, the initiator is preferably azodiisobutyronitrile (AIBN)；The quality of the initiator is preferably
The 1~5% of polyethyleneglycol diacrylate quality, further preferably 1.5~3.5%.
In the present invention, lithium salt solution lithium in aforementioned phosphate iron lithium/gelled electrolyte composite material preparation method
It is voluntarily chosen within the scope of salting liquid, details are not described herein.
The present invention also provides a kind of preparation methods of solid state lithium battery, include the following steps；
(I) LiFePO4 described in techniques described above scheme/gel electrolyte composite positive pole or above-mentioned technical side
The LiFePO4 that preparation method described in case is prepared/gel electrolyte composite positive pole as anode, using lithium metal as
The anode, cellulose membrane and lithium anode are set gradually, obtain cell matrix by cathode；
(II) it after injecting the electrolyte solution between the anode and lithium anode of the cell matrix, is packaged
Obtain button cell；The electrolyte solution includes polyethyleneglycol diacrylate, initiator and lithium salt solution；
(III) button cell that the step (II) obtains is heated, obtains solid state lithium battery.
In the present invention, the preparation of the solid state lithium battery preferably carries out under protection of argon gas；The embodiment of the present invention has
Body carries out in the glove box full of argon gas.
LiFePO4/gel electrolyte composite positive pole described in techniques described above scheme of the present invention or above-mentioned technology
The LiFePO4 that preparation method described in scheme is prepared/gel electrolyte composite positive pole is made as anode with lithium metal
For cathode；The anode, cellulose membrane and lithium anode are sequentially overlapped setting, obtain cell matrix.In the present invention, institute
It is consistent in above-mentioned solid state lithium battery technical solution with cellulose membrane to state cathode, details are not described herein.
The present invention is not special to the specific implementation mode for being superposed process of anode, cellulose membrane and lithium anode
It is required that using the stacked system of anode, diaphragm and cathode in solid state lithium battery well-known to those skilled in the art.
After the present invention injects the electrolyte solution between the anode and lithium anode of the cell matrix, sealed
Dress obtains button cell.In the present invention, the electrolyte solution includes that polyethyleneglycol diacrylate, initiator and lithium salts are molten
Liquid；The electrolyte solution is consistent with the electrolyte solution in aforementioned solid lithium battery technology scheme, and details are not described herein.This hair
It is bright by the electrolyte solution be injected into anode and lithium anode between when, electrolyte solution can penetrate into cellulose membrane
In hole, and it can flow out from cellulose membrane both sides and be contacted with positive and negative anodes.In the present invention, the mode of the injection is further
Preferably it is added dropwise；The electrolyte solution is added dropwise on the cellulose membrane between anode and lithium anode, the electrolysis
Matter solution penetrates into cellulose membrane both sides by the hole of cellulose membrane and is contacted respectively with anode and lithium anode.
The cellulose membrane is further preferably added on anode by the present invention, then electrolyte solution is added drop-wise to cellulose
After on film, it is superimposed lithium anode.
In the present invention, in terms of model CR2025 button cells, the injection rate of the electrolyte solution is preferably 120~
160 μ L, further preferably 140~150 μ L.
After the injection for completing electrolyte solution, the present invention is packaged to obtain to the cell matrix for being injected with electrolyte solution
Button cell.The present invention does not have particular/special requirement, use well known to those skilled in the art the specific implementation mode of the encapsulation
.
After obtaining button cell, the present invention heats the button cell, obtains solid state lithium battery.In this hair
In bright, the temperature of the heat treatment is preferably 60~70 DEG C, further preferably 62~65 DEG C；The time of the heat treatment
Preferably 2~6h, further preferably 2.5~5h, more preferably 3~4h.The present invention is located in the heat-treatment process
Electrolyte solution between anode and lithium anode is cured, and obtains solid state lithium battery.In an embodiment of the present invention, institute
Heat treatment is stated specifically to carry out in an oven.
With reference to embodiment to LiFePO4 provided by the invention/gel electrolyte composite positive pole and its preparation side
Method and solid state lithium battery and preparation method thereof are described in detail, but they cannot be interpreted as to the scope of the present invention
Restriction.
Embodiment 1
The preparation of LiFePO4/gel electrolyte anode composite：
(1) by LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate monomer (PEGDA), photoinitiator and lithium
Ion electrolyte is mixed and is stirred with anhydrous acetonitrile, obtains homogeneous slurry.Wherein, the grain size of LiFePO 4 powder is 200
The mass ratio of~800nm, LiFePO 4 powder and conductive black (Super P) is 3:1；The relative molecular mass of PEGDA is
400；
Lithium-ion electrolyte is 1mol L-1LiPF6Electrolyte, solvent are that volume ratio is 1:1 ethylene carbonate (EC)
With diethyl carbonate (DEC) mixed solvent；The molar ratio of lithium ion and-CCO- segments in PEGDA monomers in lithium-ion electrolyte
It is 7:1, the mass ratio of lithium salts and LiFePO4 is 1 in lithium-ion electrolyte:8；Photoinitiator uses 2- hydroxy-2-methyls -1-
Phenyl -1- acetone (HMPP), the mass ratio that photoinitiator accounts for PEGDA are 1%, the volume of anhydrous acetonitrile and LiFePO 4 powder
Mass ratio is 0.8mL：1g；
(2) according to LiFePO 4 powder in homogeneous slurry, conductive black, polyethyleneglycol diacrylate, photoinitiator and
The gross mass meter of lithium salt solution, by obtained homogeneous slurry according to 0.6g/cm2Ratio uniform is coated on aluminium flake collector；
(3) the aluminium flake collector for being coated with slurry is placed under ultraviolet light and irradiates 10 minutes, it is ensured that PEGDA's is completely poly-
It closes, while vaporing away acetonitrile solvent, obtain LiFePO4/gel electrolyte composite positive pole.
The preparation of solid state lithium battery：
(I) PEGDA, initiator and lithium-ion electrolyte are mixed and stirred for, obtain electrolyte solution, wherein
Mass fractions of the PEGDA in electrolyte mixed solution is 5%, and initiator uses azodiisobutyronitrile (AIBN), initiator
Quality accounts for the 1% of PEGDA mass；
(II) by aforementioned obtained LiFePO4/gel electrolyte anode composite, cellulose membrane (NKK), metal lithium sheet according to
Secondary superposition, and between the electrolyte solution injection positive and negative anodes that 120 μ L steps (I) are obtained, be packaged to obtain button cell, pole
Piece is superimposed and cell package process carries out all in the glove box full of argon gas；
(III) button cell obtained by step (II) is placed in 60 DEG C of heating 2h in baking oven, so that electrolyte solution is occurred solid
Change obtains solid state lithium battery.
The present embodiment obtains LiFePO4/SEM photograph of the gel electrolyte anode composite under low power and high power respectively such as
Shown in Fig. 1 (a), (b).One layer of electrolyte has uniformly been wrapped up in lithium iron phosphate particles as seen from Figure 1, and has been filled with particle
Between hole, this structure can substantially increase the contact area of LiFePO4 and electrolyte so that LiFePO4 with
Quick ion exchange can occur for electrolyte.
The LiFePO4 that the present embodiment obtains/gel electrolyte anode composite carries out tem observation, and the results are shown in Figure 2, can
It is closely combined between electrolyte and lithium iron phosphate particles with seeing.
SEM observations are carried out to the solid state lithium battery that the present embodiment obtains, Fig. 3 is that LiFePO4/gel electrolyte is compound just
The interface SEM of pole and gel electrolyte layer schemes, it can be seen that entire electrolyte layer has closely been bonded LiFePO4/gel electrolyte
Matter anode composite ensure that lithium ion transport channel enough between electrode and electrolyte.
Constant current charge-discharge test is carried out to the solid state lithium battery of preparation, charging/discharging voltage section is 4.0V~2.5V.Fig. 4 is
The high rate performance figure of solid state lithium battery, it can be seen from the figure that solid state lithium battery is in 0.1C, 0.2C, 0.5C, 1C, 2C and 5C
Capacity is respectively 155.2mAh g under current density-1、153.1mAh g-1、143.1mAh g-1、131.2mAh g-1、111.3mAh
g-1With 72mAh g-1, show excellent high rate performance.
Fig. 5 is cycle performance figure of the solid state lithium battery under 1C current densities, it is seen from fig 5 that solid state lithium battery exists
Under the current density of 0.5C, still there is 87.3% capacity to keep after recycling 100 times, coulombic efficiency is maintained at 99.5% or more, table
Reveal good cyclical stability.
Fig. 6 is the electrochemical impedance spectrogram before solid state lithium battery recycles, after recycling 100 times and after recycling 200 times, from figure
It can be seen that the Charge-transfer resistance (interface impedance) of battery is before cycle, after recycling 100 times, respectively 85 after recycling 200 times
Ω, 114 Ω, 153 Ω, the interface impedance of battery is smaller before recycling, and shows the structure of LiFePO4/gel electrolyte anode composite
Interface resistance is significantly reduced, improves contact of the electrode with electrolyte, and interface impedance of the battery in cyclic process becomes
Change less, illustrates that the solid state lithium battery constructs stable electrode/electrolyte interface, and there is excellent cyclical stability.
Embodiment 2
The preparation of LiFePO4/gel electrolyte anode composite：
(1) by LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate monomer (PEGDA), photoinitiator and lithium
Ion electrolyte is mixed and is stirred with anhydrous acetonitrile, obtains homogeneous slurry.Wherein, the grain size of LiFePO 4 powder is 200
The mass ratio of~800nm, LiFePO 4 powder and conductive black (Super P) is 7:2；The relative molecular mass of PEGDA is
600；
Lithium-ion electrolyte is 1mol L-1LiClO4Electrolyte, solvent are that volume ratio is 1:1 ethylene carbonate (EC)
With dimethyl carbonate (DMC) mixed solvent；The molar ratio of lithium ion and-CCO- segments in PEGDA monomers in lithium-ion electrolyte
It is 8:1, the mass ratio of lithium salts and LiFePO4 is 1 in lithium-ion electrolyte:20；Photoinitiator uses 2- hydroxy-2-methyls -1-
Phenyl -1- acetone (HMPP), the mass ratio that photoinitiator accounts for PEGDA are 1%, the volume of anhydrous acetonitrile and LiFePO 4 powder
Mass ratio is 1.2mL：1g；
(2) according to LiFePO 4 powder in homogeneous slurry, conductive black, polyethyleneglycol diacrylate, photoinitiator and
The gross mass meter of lithium salt solution, by obtained homogeneous slurry according to 1.2g/cm2Ratio uniform is coated on aluminium flake collector；
(3) the aluminium flake collector for being coated with slurry is placed under ultraviolet light and irradiates 20 minutes, it is ensured that PEGDA's is completely poly-
It closes, while vaporing away acetonitrile solvent, obtain LiFePO4/gel electrolyte composite positive pole.
The preparation of solid state lithium battery：
(I) PEGDA, initiator and lithium-ion electrolyte are mixed and stirred for, obtain electrolyte solution, wherein
Mass fractions of the PEGDA in electrolyte mixed solution is 10%, and initiator uses azodiisobutyronitrile (AIBN), initiator
Quality accounts for the 2% of PEGDA mass；
(II) by aforementioned obtained LiFePO4/gel electrolyte anode composite, cellulose membrane (NKK), metal lithium sheet according to
Secondary superposition, and between the electrolyte solution injection positive and negative anodes that 140 μ L steps (I) are obtained, be packaged to obtain button cell, pole
Piece is superimposed and cell package process carries out all in the glove box full of argon gas；
(III) button cell obtained by step (II) is placed in 65 DEG C of heating 4h in baking oven, so that electrolyte solution is occurred solid
Change obtains solid state lithium battery.
The solid state lithium battery obtained to the present embodiment carries out constant current charge-discharge test, charging/discharging voltage section be 4.0V~
2.5V.Specific capacity of the solid state lithium battery under the current density of 0.1C, 0.2C, 0.5C, 1C, 2C and 5C is respectively 153.7mAh
g-1、151.8mAh g-1、141.6mAhg-1、130.9mAh g-1、110.1mAh g-1With 69.3mAh g-1, show excellent
High rate performance.
Solid state lithium battery is carried out to recycle-specific capacity test, can learn solid state lithium battery under the current density of 0.5C,
Still there is 86.5% capacity to keep after recycling 100 times, coulombic efficiency is maintained at 99.5% or more, shows good stable circulation
Property.
The electrochemical impedance test under the conditions of different cycle-indexes is carried out to solid state lithium battery, can obtain the solid state lithium battery
Charge-transfer resistance (interface impedance) before cycle, cycle 100 times after, cycle 200 times after be respectively 87 Ω, 121 Ω, 167 Ω,
The interface impedance of battery is smaller before cycle, shows that the structure of LiFePO4/gel electrolyte anode composite significantly reduces interface
Resistance improves contact of the electrode with electrolyte, and interface impedance variation of the battery in cyclic process is little, illustrates that this is solid
State lithium battery constructs stable electrode/electrolyte interface, and has excellent cyclical stability.
Embodiment 3
The preparation of LiFePO4/gel electrolyte anode composite：
(1) by LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate monomer (PEGDA), photoinitiator and lithium
Ion electrolyte is mixed and is stirred with anhydrous acetonitrile, obtains homogeneous slurry.Wherein, the grain size of LiFePO 4 powder is 200
The mass ratio of~800nm, LiFePO 4 powder and conductive black (Super P) is 4:1；The relative molecular mass of PEGDA is
1000；
Lithium-ion electrolyte is 1mol L-1LiTFSi electrolyte, solvent is that volume ratio is 1:1 ethylene carbonate (EC)
With dimethyl carbonate (DMC) mixed solvent；The molar ratio of lithium ion and-CCO- segments in PEGDA monomers in lithium-ion electrolyte
It is 9:1, the mass ratio of lithium salts and LiFePO4 is 1 in lithium-ion electrolyte:70；Photoinitiator uses 2- hydroxy-2-methyls -1-
Phenyl -1- acetone (HMPP), the mass ratio that photoinitiator accounts for PEGDA are 5%, the volume of anhydrous acetonitrile and LiFePO 4 powder
Mass ratio is 2mL：1g；
(2) according to LiFePO 4 powder in homogeneous slurry, conductive black, polyethyleneglycol diacrylate, photoinitiator and
The gross mass meter of lithium salt solution, by obtained homogeneous slurry according to 1.8g/cm2Ratio uniform is coated on aluminium flake collector；
(3) the aluminium flake collector for being coated with slurry is placed under ultraviolet light and irradiates 30 minutes, it is ensured that PEGDA's is completely poly-
It closes, while vaporing away acetonitrile solvent, obtain LiFePO4/gel electrolyte composite positive pole.
The preparation of solid state lithium battery：
(I) PEGDA, initiator and lithium-ion electrolyte are mixed and stirred for, obtain electrolyte solution, wherein
Mass fractions of the PEGDA in electrolyte mixed solution is 20%, and initiator uses azodiisobutyronitrile (AIBN), initiator
Quality accounts for the 5% of PEGDA mass；
(II) by aforementioned obtained LiFePO4/gel electrolyte anode composite, cellulose membrane (NKK), metal lithium sheet according to
Secondary superposition, and between the electrolyte solution injection positive and negative anodes that 160 μ L steps (I) are obtained, be packaged to obtain button cell, pole
Piece is superimposed and cell package process carries out all in the glove box full of argon gas；
(III) button cell obtained by step (II) is placed in 70 DEG C of heating 6h in baking oven, so that electrolyte solution is occurred solid
Change obtains solid state lithium battery.
The solid state lithium battery obtained to the present embodiment carries out constant current charge-discharge test, charging/discharging voltage section be 4.0V~
2.5V.Specific capacity of the solid state lithium battery under the current density of 0.1C, 0.2C, 0.5C, 1C, 2C and 5C is respectively 153.2mAh
g-1、150.9mAh g-1、140.4mAh g-1、127.1mAh g-1、106.5mAh g-1With 65.7mAh g-1, show excellent
High rate performance.
Recycle-specific capacity test to solid state lithium battery, can learn the solid state lithium battery 0.5C current density
Under, still there is 83.4% capacity to keep after recycling 100 times, coulombic efficiency is maintained at 99.5% or more, shows good cycle
Stability.
The electrochemical impedance test under the conditions of different cycle-indexes is carried out to solid state lithium battery, can obtain the solid state lithium battery
Charge-transfer resistance (interface impedance) before cycle, cycle 100 times after, cycle 200 times after be respectively 89 Ω, 125 Ω, 173 Ω,
The interface impedance of battery is smaller before cycle, shows that the structure of LiFePO4/gel electrolyte anode composite significantly reduces interface
Resistance improves contact of the electrode with electrolyte, and interface impedance variation of the battery in cyclic process is little, illustrates that this is solid
State lithium battery constructs stable electrode/electrolyte interface, and has excellent cyclical stability.
Above example the result shows that, method provided by the invention is simple, is by a cured method of step ultraviolet light
LiFePO4/gel electrolyte anode composite can be prepared；And solid state lithium battery can be prepared by cured in place method, is made
Preparation Method is simply controllable, can with modern commercial lithium ion battery produce coating technique be combined, convenient for large-scale production with
Industrialization.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of LiFePO4/gel electrolyte composite positive pole, including collector and it is coated on the collection liquid surface
Active material composite；
The active material composite includes LiFePO 4 powder, conductive black and is wrapped in LiFePO 4 powder and conductive charcoal
The gel electrolyte on black surface；
The gel electrolyte contains the polyethyleneglycol diacrylate and solidification lithium salts electrolyte of polymerization.
2. LiFePO4 according to claim 1/gel electrolyte composite positive pole, which is characterized in that the phosphoric acid
The mass ratio of iron powder for lithium and conductive black is preferably (3~4):1；
The molar ratio of-CCO- segments is in elemental lithium and the polyethyleneglycol diacrylate of polymerization in the solidification lithium salts electrolyte
(7~9)：1；
The mass ratio of lithium salts and LiFePO 4 powder is 1 in the solidification lithium salts electrolyte:(8~70)；
The active material composite is 0.6~1.8g/cm in the covering amount of collection liquid surface2。
3. a kind of preparation method of LiFePO4/gel electrolyte composite positive pole, includes the following steps：
(1) by LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate, photoinitiator, lithium salt solution and dispersion solvent
Homogeneous is mixed, homogeneous slurry is obtained；
(2) the homogeneous slurry in the step (1) is coated in collection liquid surface, obtains pole piece；
(3) pole piece for obtaining the step (2) carries out ultraviolet light solidification, obtains LiFePO4/gel electrolyte anode composite
Material.
4. preparation method according to claim 3, which is characterized in that the grain size of the LiFePO 4 powder be 200~
800nm；
The relative molecular mass of the polyethyleneglycol diacrylate is 400~1000；
The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone；
The dispersion solvent is anhydrous acetonitrile.
5. preparation method according to claim 3 or 4, which is characterized in that the LiFePO 4 powder and conductive black
Mass ratio is (3~4):1；
The molar ratio of lithium ion and-CCO- segments in polyethyleneglycol diacrylate is (7~9) in the lithium salt solution：1；
The mass ratio of lithium salts and LiFePO 4 powder is 1 in the lithium salt solution:(8~70)；
The quality of the photoinitiator is the 1%~5% of polyethyleneglycol diacrylate quality；
The mass ratio of the dispersion solvent volume and LiFePO 4 powder is (0.8~2) mL：1g.
6. preparation method according to claim 3, which is characterized in that lithium salts is LiTFSI, LiClO in the lithium salt solution4
And LiPF6In it is one or more；
Solvent includes ethylene carbonate and secondary solvent in the lithium salt solution, and the secondary solvent is diethyl carbonate, carbonic acid
It is one or more in dimethyl ester and makrolon.
7. preparation method according to claim 3, which is characterized in that the coated weight coated in the step (2) is with homogeneous
The gross mass meter of LiFePO 4 powder, conductive black, polyethyleneglycol diacrylate, photoinitiator and lithium salt solution in slurry,
For 0.6~1.8g/cm2。
8. a kind of solid state lithium battery, including the anode, cellulose membrane and the lithium anode that set gradually, the material of the anode are
Any one of claim 1~2 any one of them LiFePO4/gel electrolyte composite positive pole or claim 3~7 institute
State LiFePO4/gel electrolyte composite positive pole that preparation method is prepared；
Contain electrolyte between the anode and lithium anode, the electrolyte be include polyethyleneglycol diacrylate, draw
Send out the solidfied material of the electrolyte solution of agent and lithium salt solution.
9. a kind of preparation method of solid state lithium battery according to any one of claims 8, includes the following steps：
(I) with claim 1~2 any one of them LiFePO4/gel electrolyte composite positive pole or claim 3~
LiFePO4/gel electrolyte composite positive pole that any one of 7 preparation methods are prepared is as anode, with lithium metal
As cathode, the anode, cellulose membrane and lithium anode are set gradually, cell matrix is obtained；
(II) it after injecting the electrolyte solution between the anode and lithium anode of the cell matrix, is packaged to obtain
Button cell；The electrolyte solution includes polyethyleneglycol diacrylate, initiator and lithium salt solution；
(III) button cell that the step (II) obtains is heated, obtains solid state lithium battery.
10. preparation method according to claim 9, which is characterized in that the temperature of heat treatment is in the step (III)
60~70 DEG C, the time of heat treatment is 2~6h.
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| CN109817910A (en) * | 2019-01-09 | 2019-05-28 | 蜂巢能源科技有限公司 | Positive electrode and preparation method thereof for solid lithium ion battery |
| CN110061207A (en) * | 2019-03-29 | 2019-07-26 | 中国人民解放军国防科技大学 | Nickel-cobalt-aluminum ternary cathode material coated with chelate copolymer gel layer and preparation method and application thereof |
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