CN116014238A - Semi-solid electrolyte, synthesis method and application thereof, and semi-solid lithium battery - Google Patents
Semi-solid electrolyte, synthesis method and application thereof, and semi-solid lithium battery Download PDFInfo
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- CN116014238A CN116014238A CN202310119870.XA CN202310119870A CN116014238A CN 116014238 A CN116014238 A CN 116014238A CN 202310119870 A CN202310119870 A CN 202310119870A CN 116014238 A CN116014238 A CN 116014238A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 100
- 239000007787 solid Substances 0.000 title claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title description 2
- 239000002608 ionic liquid Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 150000001408 amides Chemical class 0.000 claims abstract description 21
- 239000011256 inorganic filler Substances 0.000 claims abstract description 21
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims description 18
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- GMQVFHZSXKJCIV-UHFFFAOYSA-N 2,2,2-trifluoro-n-(2,2,2-trifluoroacetyl)acetamide Chemical compound FC(F)(F)C(=O)NC(=O)C(F)(F)F GMQVFHZSXKJCIV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 3
- 229910020724 Li0.34La0.51TiO2.94 Inorganic materials 0.000 claims description 3
- 229910010406 Li1.2Al0.2Ti1.8(PO4)3 Inorganic materials 0.000 claims description 3
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 claims description 3
- 229910012305 LiPON Inorganic materials 0.000 claims description 3
- 229910013439 LiZr Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- RWRIWBAIICGTTQ-UHFFFAOYSA-N anhydrous difluoromethane Natural products FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 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 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000005677 organic carbonates Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical compound CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
Classifications
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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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Abstract
The invention belongs to the field of batteries, and particularly relates to a semi-solid electrolyte, a preparation method and application thereof, and a semi-solid lithium battery. The invention provides a semi-solid electrolyte, which comprises a polymer, lithium salt, ionic liquid, inorganic filler and fluorinated amide solvent. The semi-solid electrolyte provided by the invention is Li when being used in a lithium battery + The transmission of the polymer is faster, the ionic conductivity is higher, and the electrochemical performance is excellent.
Description
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to a semi-solid electrolyte, a preparation method and application thereof, and a semi-solid lithium battery.
Background
With the development of social economy, lithium batteries have been widely used in portable electronic products such as mobile phones, portable computers, video cameras, etc., and large-capacity lithium secondary batteries have been tried in electric vehicles, which will become one of the main power sources of electric vehicles. With the continuous expansion of the application field of lithium secondary batteries, the safety performance thereof is becoming more important.
The electrolyte is an important component of a lithium ion battery, plays roles in transmitting lithium ions and conducting current, is mainly an organic carbonate system, has the defects of easy liquid leakage, inflammability, easy explosion, easy volatilization and the like, and simultaneously is easy to react with an active lithium metal cathode in the long-cycle process of the lithium battery, continuously consumes electrode materials and the electrolyte, induces the generation of lithium dendrites, and can lead to continuous dissolution of transition metal ions or active substances with the positive electrode to influence the physical and chemical properties of the cathode and the electrolyte, thereby causing serious safety problems. The replacement of flammable and explosive organic liquid electrolytes with nonflammable solid electrolytes is one of the effective ways to improve the safety performance of batteries. The solid electrolyte has an ultra-high mechanical strength and is believed to be effective in blocking lithium dendrite growth. However, the electrode-solid electrolyte has problems of poor interface contact, large interface impedance, low interface compatibility, and the like. The above problems can be solved to a large extent by considering the use of a semi-solid electrolyte to improve the interfacial contact problem.
At present, one of the methods for synthesizing the semi-solid electrolyte is to immerse and absorb the organic carbonate electrolyte, but the electrolyte is unstable to the electrode with strong oxidation/reduction property, side reaction is easy to occur, the electrolyte is continuously consumed, if the immersed amount is excessive, part of the unfixed electrolyte still remains on the components, and potential safety hazards are easy to form in the battery circulation process.
Disclosure of Invention
In view of the above, the present invention is directed to a semi-solid electrolyte, a method for preparing the same, an application of the same, and a semi-solid lithium battery, wherein the semi-solid electrolyte is Li when used in the lithium battery + The transmission of the polymer is faster, the ionic conductivity is higher, and the electrochemical performance is excellent.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a semi-solid electrolyte, which comprises a polymer, lithium salt, ionic liquid, inorganic filler and fluorinated amide solvent.
Preferably, the ionic liquid comprises one or more of pyrrolidine ionic liquid, imidazole ionic liquid, difluoromethane sulfonyl imide and tetrafluoroboric acid.
Preferably, the fluorinated amide-based solvent comprises 2, 3-N, N-diethyl-tetrafluoropropionamide, 2-trifluoro-N, N-dimethylacetamide, 1, 2-tetrafluoro-N, one or more of N-dimethylacetamide, 3-trifluoro-N, N-dimethylpropionamide and bistrifluoroacetamide.
Preferably, the polymer comprises one or more of polyacrylonitrile, polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride and chlorinated polyethylene.
Preferably, the inorganic filler comprises LiPON, li 7 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 5 La 3 Zr 2 O 12 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 、LiZr 2 (PO 4 ) 3 、Li 0.34 La 0.51 TiO 2.94 、Li 0.38 La 0.56 Ti 0.99 Al 0.01 O 3 And Li (lithium) 6.4 La 3 Zr 1.4 Ta 0.6 O 12 One or more of them.
Preferably, the mass of the inorganic filler is 10 to 60% of the mass of the semi-solid electrolyte.
Preferably, the mass of the polymer is 30-70% of the total mass of the fluorinated amide solvent and the ionic liquid.
The invention also provides a preparation method of the semi-solid electrolyte, which comprises the following steps:
and mixing the polymer, lithium salt, ionic liquid, inorganic filler and fluorinated amide solvent to obtain the semi-solid electrolyte.
The invention also provides application of the semi-solid electrolyte or the semi-solid electrolyte prepared by the preparation method in a lithium battery.
The invention also provides a semi-solid lithium battery, which comprises a positive electrode, a negative electrode and a semi-solid electrolyte diaphragm; the positive electrode comprises lithium iron phosphate, ternary material or lithium nickel manganese oxide; the negative electrode is lithium or lithium alloy; the semi-solid electrolyte membrane is made of the semi-solid electrolyte.
The invention provides a semi-solid electrolyte, which comprises a polymer, lithium salt, ionic liquid, inorganic filler and fluorinated amide solvent. The invention selects the fluorinated amide solvent as the solvent in the semi-solid electrolyte, has high dielectric constant, high solubility to polymer and lithium salt, does not react with groups or ions in the polymer and inorganic filler, and is beneficial to accelerating Li + And improves the ionic conductivity. In addition, the fluorinated amide solvent has high thermal stability and chemical stability, fluorine atoms in the fluorinated amide solvent have strong electron-withdrawing induction effect, and a fluorinated chain can reduce the LUMO value, so that the fluorinated amide solvent is subjected to preferential reduction and decomposition on a lithium negative electrode to generate a plurality of fluorinated mesophase matters, thereby stabilizing an interface semi-solid electrolyte membrane, protecting the lithium negative electrode and improving the safety of the semi-solid electrolyte membrane. Meanwhile, the ionic liquid is introduced into the semi-solid electrolyte, is in a liquid state at room temperature, has the advantages of flame retardance, lightning, high boiling point and difficult volatilization, has a wide electrochemical window, can be suitable for lithium batteries of high-voltage systems, and can reduce interaction of hydrogen bonds due to fluorinated chains in fluorinated amide solvents although the ionic liquid has high viscosity, so that the viscosity of the ionic liquid is reduced, and Li is improved + Thereby improving the ion conductivity of the semi-solid electrolyte.
The invention provides a preparation method of the semi-solid electrolyte, which comprises the following steps: and mixing the polymer, lithium salt, ionic liquid, inorganic filler and fluorinated amide solvent to obtain the semi-solid electrolyte. The semi-solid electrolyte is obtained by adopting the one-step mixing method, and compared with other preparation methods, the preparation method provided by the invention has the advantages of simple steps, short time consumption and easiness in realizing industrialization.
Drawings
Fig. 1 is an ion conductivity diagram of a semi-solid electrolyte of comparative example 1;
fig. 2 is an ion conductivity diagram of the semi-solid electrolyte of example 1;
fig. 3 is a charge-discharge graph of the semi-solid battery of comparative application example 1 at 0.1C;
fig. 4 is a cycle performance chart of the semi-solid battery of comparative application example 1;
fig. 5 is a charge-discharge graph of the semi-solid battery of application example 1 at 0.1C;
fig. 6 is a cycle performance chart of the semi-solid battery of application example 1;
fig. 7 is a charge-discharge graph of the semi-solid battery of application example 2 at 0.1C;
fig. 8 is a cycle performance chart of the semi-solid battery of application example 2;
fig. 9 is a charge-discharge graph of the semi-solid battery of application example 3 at 0.1C;
fig. 10 is a cycle performance chart of the semi-solid battery of application example 3;
fig. 11 is a charge-discharge graph of the semi-solid battery of application example 4 at 0.1C;
fig. 12 is a cycle performance chart of the semi-solid battery of application example 4;
fig. 13 is a charge-discharge graph of the semi-solid battery of application example 5 at 0.1C;
fig. 14 is a cycle performance chart of the semi-solid battery of application example 5;
fig. 15 is a charge-discharge graph of the semi-solid battery of application example 6 at 0.1C;
fig. 16 is a cycle performance chart of the semi-solid battery of application example 6.
Detailed Description
The invention provides a semi-solid electrolyte, which comprises a polymer, lithium salt, ionic liquid, inorganic filler and fluorinated amide solvent.
In the present invention, the components are commercially available products well known to those skilled in the art unless specified otherwise.
In the present invention, the polymer preferably includes one or more of polyacrylonitrile, polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride, and chlorinated polyethylene, more preferably polyvinylidene fluoride-hexafluoropropylene. In the present invention, the weight average molecular weight of the polymer is preferably 400 to 500g/mol, more preferably 400 to 450g/mol.
In the present invention, the fluorinated amide-based solvent preferably includes 2, 3-N, N-diethyl-tetrafluoropropionamide, 2-trifluoro-N, N-dimethylacetamide, 1, 2-tetrafluoro-N, one or more of N-dimethylacetamide, 3-trifluoro-N, N-dimethylpropionamide and bistrifluoroacetamide, more preferably 2, 3-N, N-diethyl-tetrafluoropropionamide.
In the invention, the ionic liquid preferably comprises one or more of pyrrolidine ionic liquid, imidazole ionic liquid, difluoromethane sulfonyl imide and tetrafluoroboric acid; the pyrrolidine ionic liquid preferably comprises N-alkyl-N-methyl pyrrolidine; the imidazole ionic liquid preferably comprises 1-vinyl-3-methylimidazole, 1-alkyl-3-methylimidazole bis-fluoromethanesulfonyl imide and 1-alkyl-3-methylimidazole trifluoro-methanesulfonyl imide. In the present invention, the alkyl group in the pyrrolidine-based ionic liquid preferably includes an ethyl group, a propyl group, a butyl group, a hexyl group or an octyl group, and more preferably an ethyl group. The alkyl group in the imidazole-based ionic liquid preferably includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, or an octadecyl group, and more preferably a methyl group or an ethyl group.
In the present invention, the lithium salt preferably includes LiTFSI, liFSI, liBOB, liDFOB and LiPF 6 More preferably LiTFSI or LiBOB.
In the present invention, the inorganic filler preferably includes LiPON, li 7 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 5 La 3 Zr 2 O 12 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 、LiZr 2 (PO 4 ) 3 、Li 0.34 La 0.51 TiO 2.94 、Li 0.38 La 0.56 Ti 0.99 Al 0.01 O 3 And Li (lithium) 6.4 La 3 Zr 1.4 Ta 0.6 O 12 One or more of them, more preferably Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 。
In the present invention, the mass of the polymer is preferably 30 to 70% of the total mass of the fluorinated amide-based solvent and the ionic liquid, more preferably 40 to 50%. In the present invention, the mass ratio of the fluorinated amide solvent to the ionic liquid is preferably 1:1 to 1:5, more preferably 1:2 to 1:4. In the present invention, the concentration of the lithium salt in the semi-solid electrolyte is preferably 0.5 to 5M, more preferably 1 to 4M. In the present invention, the mass of the inorganic filler is preferably 10 to 60% of the mass of the semi-solid electrolyte, more preferably 40 to 50%.
The invention also provides a preparation method of the semi-solid electrolyte, which comprises the following steps:
and mixing the polymer, lithium salt, ionic liquid, inorganic filler and fluorinated amide solvent to obtain the semi-solid electrolyte.
In the present invention, the mixing is preferably a first mixing of the polymer, the lithium salt, the ionic liquid and the fluorinated amide-type solvent, and a second mixing of the resulting mixture and the inorganic filler.
In the present invention, the first mixing means is preferably magnetic stirring, and the rotation speed of the magnetic stirring is preferably 100 to 200rpm, more preferably 100 to 150rpm, and the time is preferably 4 to 10 hours, more preferably 5 to 8 hours.
In the present invention, the second mixing means is preferably magnetic stirring, and the rotation speed of the magnetic stirring is preferably 800 to 1200rpm, more preferably 900 to 1000rpm, and the time is preferably 2 to 6 hours, more preferably 3 to 5 hours.
The invention also provides application of the semi-solid electrolyte in a lithium battery.
The invention provides a semi-solid lithium battery, which comprises a positive electrode, a negative electrode and a semi-solid electrolyte diaphragm;
the positive electrode preferably comprises lithium iron phosphate, ternary material or lithium nickel manganese oxide; the ternary material preferably includes NMC622.
The negative electrode is preferably lithium or a lithium alloy, more preferably lithium; the lithium alloy preferably includes a lithium manganese alloy, a lithium boron alloy, a lithium aluminum alloy, or a lithium indium alloy, more preferably a lithium manganese alloy.
In the invention, the material of the semi-solid electrolyte membrane is the semi-solid electrolyte. In the present invention, the thickness of the semi-solid electrolyte membrane is preferably 40 to 100 μm, more preferably 50 to 80 μm in the present invention.
In the present invention, the preparation of the semi-solid electrolyte membrane preferably includes hot-pressing the semi-solid electrolyte membrane to obtain the semi-solid electrolyte membrane.
In the present invention, the conditions for the hot press film formation preferably include: the temperature is preferably 60 to 150 ℃, more preferably 120 to 130 ℃, the pressure is preferably 600 to 1000Pa, more preferably 800 to 900Pa, and the time is preferably 3 to 5min, more preferably 4 to 5min.
The lithium ion battery composite gel membrane, the preparation method and the application thereof provided by the invention are described in detail below by combining examples, but the lithium ion battery composite gel membrane and the preparation method and the application thereof cannot be understood as limiting the protection scope of the invention.
Example 1
The polymer PVDF-HFP, the ionic liquid EMIMTFSI and the lithium salt LiTFSI were dissolved in 2, 2-trifluoro-N, N-dimethylacetamide and magnetically stirred for 5 hours, and then an inorganic filler (Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 ) Adding the electrolyte into the electrolyte, and magnetically stirring the electrolyte for 5 hours to obtain a semi-solid electrolyte;
in the above semi-solid electrolyte: the volume ratio of the 2, 2-trifluoro-N, N-dimethylacetamide to the ionic liquid is 1:1; the mass of the polymer is 40% of the total mass of the 2, 2-trifluoro-N, N-dimethylacetamide solvent and the ionic liquid; the concentration of lithium salt in the semi-solid electrolyte is 1M; the mass concentration of the inorganic filler in the semi-solid electrolyte is 40%.
Example 2
The only difference from example 1 is that: 2, 2-trifluoro-N, N-dimethylacetamide was replaced with 2, 3-N, N-diethyl-tetrafluoropropionamide.
Example 3
The only difference from example 1 is that: liTFSI is replaced with LiBOB.
Example 4
The only difference from example 1 is that: the mass concentration of the inorganic filler in the semi-solid electrolyte is 10%.
Example 5
The only difference from example 1 is that: the mass concentration of the inorganic filler in the semi-solid electrolyte is 60 percent.
Example 6
The only difference from example 1 is that: the concentration of LiTFSI in the semi-solid electrolyte was 3M.
Comparative example 1
The only difference from example 1 is that: 2, 2-trifluoro-N, N-dimethylacetamide was replaced with acetone.
Application example 1
The semi-solid electrolyte prepared in the example 1 is hot-pressed for 4min to form a film at 120 ℃ and 800Pa, and a semi-solid electrolyte diaphragm is obtained;
cutting the semi-solid electrolyte membrane into small discs with the diameter of 16mm, and assembling the small discs with positive electrode material NMC622 and negative electrode material Li metal to form NMC 622/semi-solid electrolyte/Li full battery.
Application example 2
The semi-solid electrolyte prepared in the example 2 is hot-pressed for 4min to form a film at the temperature of 100 ℃ and the pressure of 1000Pa, so as to obtain a semi-solid electrolyte diaphragm;
cutting the semi-solid electrolyte membrane into small discs with the diameter of 16mm, and assembling the small discs with positive electrode material NMC622 and negative electrode material Li metal to form NMC 622/semi-solid electrolyte/Li full battery.
Application example 3
The semi-solid electrolyte prepared in the example 3 is hot-pressed for 5min to form a film at 120 ℃ and 600Pa, and a semi-solid electrolyte diaphragm is obtained;
cutting the semi-solid electrolyte membrane into small discs with the diameter of 16mm, and assembling the small discs with positive electrode material NMC622 and negative electrode material Li metal to form NMC 622/semi-solid electrolyte/Li full battery.
Application example 4
The semi-solid electrolyte prepared in the example 4 is hot-pressed for 3min to form a film at 150 ℃ and 800Pa, and a semi-solid electrolyte diaphragm is obtained;
cutting the semi-solid electrolyte membrane into small discs with the diameter of 16mm, and assembling the small discs with positive electrode material NMC622 and negative electrode material Li metal to form NMC 622/semi-solid electrolyte/Li full battery.
Application example 5
The semi-solid electrolyte prepared in the example 5 is hot-pressed for 5min to form a film at 80 ℃ and 800Pa, and a semi-solid electrolyte diaphragm is obtained;
cutting the semi-solid electrolyte membrane into small discs with the diameter of 16mm, and assembling the small discs with positive electrode material NMC622 and negative electrode material Li metal to form NMC 622/semi-solid electrolyte/Li full battery.
Application example 6
The semi-solid electrolyte prepared in the example 6 is hot-pressed for 4min to form a film at 80 ℃ and 1000Pa, and a semi-solid electrolyte diaphragm is obtained;
cutting the semi-solid electrolyte membrane into small discs with the diameter of 16mm, and assembling the small discs with positive electrode material NMC622 and negative electrode material Li metal to form NMC 622/semi-solid electrolyte/Li full battery.
Comparative application example 1
The semi-solid electrolyte prepared in the comparative application example 1 is hot-pressed for 4min to form a film at 60 ℃ and 800Pa, and a semi-solid electrolyte diaphragm is obtained;
cutting the semi-solid electrolyte membrane into small discs with the diameter of 16mm, and assembling the small discs with positive electrode material NMC622 and negative electrode material Li metal to form NMC 622/semi-solid electrolyte/Li full battery.
Test example:
ion conductivity test:
the room temperature ion conductivities of the semi-solid electrolytes prepared in comparative example 1 and example 1 were tested, and the test results are shown in fig. 1 to 2, respectively, and it can be seen from fig. 1 to 2: the conductivity of comparative example 1 was 5 x 10 -5 S/cm, conductivity of example 1 was 4.4.10 -4 S/cm, differing by an order of magnitude.
And (3) testing charge and discharge performance:
according to the invention, the NMC 622/semi-solid electrolyte/Li full battery prepared in comparative application example 1 and application examples 1-6 are subjected to charge-discharge performance and cycle performance tests, and test results are shown in figures 3-16, wherein figures 3-4 are respectively a charge-discharge curve chart and a cycle performance test chart of the semi-solid battery in comparative application example 1 at 0.1C, and as can be seen from figures 3-4: the semi-solid battery prepared in comparative application example 1 has a specific capacity of 98mAh/g after first discharge, and after 38 cycles, the capacity only remains 87mAh/g, and the capacity retention rate is 88.6%.
Fig. 5 to 6 are a charge-discharge curve chart and a cycle performance test chart of the semi-solid state battery of application example 1 at 0.1C, respectively, as can be seen from fig. 5 to 6: the semi-solid battery prepared in application example 1 has a specific capacity of 122mAh/g after initial discharge, reaches 131mAh/g after 5 times of activation, has a specific capacity of 117mAh/g after 70 times of circulation, and has a capacity retention rate of 92.9%.
Fig. 7 to 8 are a charge-discharge curve chart and a cycle performance test chart of the semi-solid state battery of application example 2 at 0.1C, respectively, as can be seen from fig. 7 to 8: the semi-solid battery prepared in application example 2 has a specific capacity of 157mAh/g after first discharge, a capacity of 139mAh/g after 90 times of circulation, and a capacity retention rate of 88.5%.
Fig. 9 to 10 are charge and discharge graphs at 0.1C of the semi-solid state battery of application example 3, respectively, as can be seen from fig. 9 to 10: the semi-solid electrolyte assembled battery prepared in application example 3 has a specific capacity of 143mAh/g for the first time, a capacity of 135mAh/g after 60 cycles, and a capacity retention rate of 94.4%.
Fig. 11 to 12 are charge and discharge graphs at 0.1C of the semi-solid state battery of application example 4, respectively, and as can be seen from fig. 11 to 12: the semi-solid battery prepared in application example 4 has a specific capacity of 121mAh/g after first discharge, a capacity of 113mAh/g after 80 cycles, and a capacity retention rate of 93.4%.
Fig. 13 to 14 are charge and discharge graphs at 0.1C of the semi-solid state battery of application example 5, respectively, as can be seen from fig. 13 to 14: the semi-solid battery prepared in application example 5 has a specific capacity of 130mAh/g after initial discharge, a capacity of 126mAh/g after 60 cycles, and a capacity retention rate of 96.9%.
Fig. 15 to 16 are charge and discharge graphs at 0.1C of the semi-solid state battery of application example 6, respectively, as can be seen from fig. 15 to 16: the semi-solid battery prepared in application example 6 has a specific capacity of 145mAh/g after first discharge, a capacity of 128mAh/g after 90 cycles, and a capacity retention rate of 88.3%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A semi-solid electrolyte, characterized in that the semi-solid electrolyte comprises a polymer, a lithium salt, an ionic liquid, an inorganic filler and a fluorinated amide solvent.
2. The semi-solid electrolyte of claim 1, wherein the ionic liquid comprises one or more of a pyrrolidine ionic liquid, an imidazole ionic liquid, a difluoromethane sulfonyl imide, and tetrafluoroboric acid.
3. The semi-solid electrolyte of claim 1, wherein the fluorinated amide solvent comprises 2, 3-N, N-diethyl-tetrafluoropropionamide, 2-trifluoro-N, one or more of N-dimethylacetamide, 1, 2-tetrafluoro-N, N-dimethylacetamide, 3-trifluoro-N, N-dimethylpropionamide and bistrifluoroacetamide.
4. The semi-solid electrolyte of claim 1, wherein the polymer comprises one or more of polyacrylonitrile, polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride, and chlorinated polyethylene.
5. The semi-solid electrolyte of claim 1, wherein the inorganic filler comprises LiPON, li 7 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 5 La 3 Zr 2 O 12 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 、LiZr 2 (PO 4 ) 3 、Li 0.34 La 0.51 TiO 2.94 、Li 0.38 La 0.56 Ti 0.99 Al 0.01 O 3 And Li (lithium) 6.4 La 3 Zr 1.4 Ta 0.6 O 12 One or more of them.
6. The semi-solid electrolyte according to claim 1 or 5, wherein the mass of the inorganic filler is 10 to 60% of the mass of the semi-solid electrolyte.
7. The semi-solid electrolyte according to claim 1, wherein the mass of the polymer is 30 to 70% of the total mass of the fluorinated amide solvent and the ionic liquid.
8. The method for preparing a semi-solid electrolyte as claimed in claim 1, comprising the steps of:
and mixing the polymer, lithium salt, ionic liquid, inorganic filler and fluorinated amide solvent to obtain the semi-solid electrolyte.
9. Use of the semi-solid electrolyte according to any one of claims 1 to 7 or the semi-solid electrolyte prepared by the preparation method according to claim 8 in lithium batteries.
10. A semi-solid lithium battery is characterized by comprising a positive electrode, a negative electrode and a semi-solid electrolyte diaphragm;
the positive electrode comprises lithium iron phosphate, ternary material or lithium nickel manganese oxide; the negative electrode is lithium or lithium alloy; the material of the semi-solid electrolyte membrane is the semi-solid electrolyte according to any one of claims 1 to 7.
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