CN111224184A - Preparation method and application of solid electrolyte interface additive of lithium ion battery - Google Patents
Preparation method and application of solid electrolyte interface additive of lithium ion battery Download PDFInfo
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- CN111224184A CN111224184A CN202010064266.8A CN202010064266A CN111224184A CN 111224184 A CN111224184 A CN 111224184A CN 202010064266 A CN202010064266 A CN 202010064266A CN 111224184 A CN111224184 A CN 111224184A
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- lithium ion
- solid electrolyte
- ion battery
- lithium
- electrolyte interface
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 253
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 238
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 212
- 239000000654 additive Substances 0.000 title claims abstract description 97
- 230000000996 additive effect Effects 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 104
- 239000002002 slurry Substances 0.000 claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000007731 hot pressing Methods 0.000 claims abstract description 5
- 239000003208 petroleum Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 31
- -1 polypropylene carbonate Polymers 0.000 claims description 23
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000011086 glassine Substances 0.000 claims description 13
- 239000000123 paper Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 8
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000002985 plastic film Substances 0.000 abstract 1
- 229920006255 plastic film Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 25
- 239000007787 solid Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011056 performance test Methods 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 5
- 239000006256 anode slurry Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 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 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 2
- 229940068886 polyethylene glycol 300 Drugs 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses a preparation method of a solid electrolyte interface additive of a lithium ion battery, which comprises the following steps: dissolving polyethylene glycol and methyl methacrylate in an ice-water bath, deoxidizing, and introducing nitrogen to initiate polymerization; adding petroleum ether to separate precipitate, washing and drying to obtain the solid electrolyte interface additive of the lithium ion battery. The invention also discloses an application of the solid electrolyte interface additive of the lithium ion battery, which comprises the following steps: dissolving the lead-free lithium secondary battery in dioxolane, and adding 2 times of nano Li by mass7La3Zr2O12Mixing into slurry, coating on one side of the solid electrolyte membrane of the lithium ion battery, and drying; pasting a lithium belt on the solid electrolyte of the lithium ion battery and coating the slurryAnd (3) sticking the positive pole piece on one surface of the material and the other surface of the material, and hot-pressing the positive pole piece in an aluminum plastic film to obtain the all-solid-state lithium ion battery. The lithium ion battery solid electrolyte interface additive prepared by the invention has the advantages of less impurities, small impedance and high mechanical strength. The all-solid-state lithium ion battery prepared by the lithium ion battery solid electrolyte interface additive has good cycle performance.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a preparation method and application of a solid electrolyte interface additive of a lithium ion battery.
Background
The lithium ion battery has the characteristics of high energy density, good cycle performance, no pollution and the like, is widely applied to consumer electronics products, and becomes a primary candidate of an energy storage system of a pure electric and hybrid electric vehicle. However, since most of the electrolytes used in the electrolyte are carbonate or ether solvents having a narrow electrochemical window, there are safety problems such as ignition and explosion due to leakage. Therefore, the solid lithium ion battery with high safety inevitably replaces part of the traditional liquid lithium ion battery. The all-solid-state lithium ion battery adopts the solid electrolyte with a solid structure, so that the defects of battery leakage and poor safety performance can be overcome, but the application of the lithium ion battery with the solid electrolyte is limited because the solid electrolyte has larger interface impedance.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium ion battery solid electrolyte interface additive and an application method thereof, so that the lithium ion battery solid electrolyte interface additive has small impedance and high mechanical strength.
The technical scheme of the invention is as follows:
a preparation method of a solid electrolyte interface additive of a lithium ion battery comprises the following steps:
the method comprises the following steps: under the ice-water bath, adding a mixture of polyethylene glycol with the molecular weight not more than 300 and methyl methacrylate into N, N-dimethylformamide or acetone for dissolving, and introducing nitrogen to remove oxygen for 5-10 min;
step two: under the condition of introducing nitrogen, adding an initiator accounting for 1-3% of the mass sum of the polyethylene glycol and the methyl methacrylate for polymerization reaction, and quenching the reaction solution to terminate the polymerization after the reaction is completed;
step three: adding petroleum ether, stirring, separating the precipitate, washing with ethanol, and drying to obtain the solid electrolyte interface additive for lithium ion battery.
According to the preparation method, firstly, under an ice-water bath, polyethylene glycol and methyl methacrylate are dissolved, and the low temperature of the ice-water bath and the nitrogen oxygen removal step can effectively avoid impurities generated by undesirable side reactions of reactants when an initiator is not added; after the reaction raw materials are fully dissolved and deoxygenated, the initiator is added to raise the reaction temperature, so that the polymerization reaction is effectively controlled, the generation of impurities in the product is avoided, and the prepared solid electrolyte interface additive for the lithium ion battery is pure. The lithium ion battery solid electrolyte interface additive prepared by the method is pure, low in impedance and high in mechanical strength.
Preferably, the mass ratio of the polyethylene glycol to the methyl methacrylate is 10: 2-5.
The application of the solid electrolyte interface additive of the lithium ion battery prepared by the method comprises the following steps:
the method comprises the following steps: dissolving the lithium ion battery solid electrolyte interface additive in dioxolane, wherein the mass of the lithium ion battery solid electrolyte interface additive is 10% of that of the dioxolane; adding nano Li 2 times of the mass of the solid electrolyte interface additive of the lithium ion battery7La3Zr2O12Mixing to obtain solid electrolyte interface additive slurry of the lithium ion battery;
lithium salt and a solid electrolyte material are mixed according to the mass ratio of 1-6: 9-4, adding the mixture into a solvent, dispersing the mixture to prepare slurry, coating the slurry on glassine release paper at the temperature of 60-130 ℃, drying and separating to obtain the solid electrolyte membrane of the lithium ion battery;
coating the prepared lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained lithium ion battery solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain a modified lithium ion battery solid electrolyte membrane;
step two: preparing a positive pole piece;
and (3) attaching a lithium belt to one surface of the prepared modified lithium ion battery solid electrolyte membrane, which is coated with the lithium ion battery solid electrolyte interface additive slurry, attaching a positive pole piece to the other surface of the modified lithium ion battery solid electrolyte membrane, and hot-pressing the positive pole piece in an aluminum plastic membrane at the temperature of 80-150 ℃ to obtain the all-solid-state lithium ion battery.
After the solid electrolyte interface additive of the lithium ion battery is coated between the solid electrolyte membrane and the lithium cathode, the wettability between the solid electrolyte and the metal lithium in the battery can be improved, and the interface impedance of the assembled blocked battery is obviously reduced.
In the first step of the invention, when the slurry of the lithium ion battery solid electrolyte interface additive is prepared, the mass of the lithium ion battery solid electrolyte interface additive is 10% of that of the dioxolane, and nano Li 2 times of the mass of the lithium ion battery solid electrolyte interface additive is added7La3Zr2O12After drying, a transition layer capable of increasing the wettability between the solid electrolyte and the metal lithium is formed on one side of the solid electrolyte membrane of the lithium ion battery close to the lithium belt, and the mass of the additive, the mass of dioxolane and the nano Li in the transition layer7La3Zr2O1The mass of the lithium ion battery is matched according to the proportion of the invention, so that in the manufactured all-solid-state lithium ion battery, lithium ions form reasonable lithium ion concentration gradient in the negative electrode, the transition layer and the solid electrolyte membrane. Since in the all-solid-state lithium ion battery, the rapid and effective conduction of lithium ions determines the performance of the battery, and if the conduction speeds of all parts are different in the conduction process of the lithium ions, the lithium ions can be locally generatedThe local enrichment reduces the transmission efficiency of the whole lithium ions on one hand and influences the electrical property of the battery; on the other hand, the accumulation of lithium ions causes the precipitation of lithium dendrites, which causes short circuits and affects the safety performance of the battery. In all-solid-state lithium ion batteries, the positive electrode, negative electrode, and solid electrolyte membrane of the battery are composed of different materials, and the conductivity of lithium ions in the different materials is different. According to the method, through the design of different concentrations of lithium ions in different parts of the battery, a reasonable lithium ion concentration gradient is formed, so that the conduction rates of the lithium ions in all parts are approximately the same, and the solid electrolyte membrane of the lithium ion battery prepared by the method has higher ionic conductivity and is not easy to generate lithium dendrites.
In addition, the lithium ion solid electrolyte membrane prepared by the method is coated with the lithium ion battery solid electrolyte interface additive, and the mechanical property of the lithium ion solid electrolyte membrane is also improved, so that the cycle performance of the prepared battery is also improved.
Preferably, the lithium ion battery solid electrolyte membrane in the step one is added with nanoscale Li7La3Zr2O12(ii) a More preferably nanoscale Li7La3Zr2O12Is 60 to 90 percent of the mass of the solid electrolyte material. Nanoscale Li7La3Zr2O12The addition of the lithium ion battery can improve the stability of the solid electrolyte material and the lithium cathode, and further improve the mechanical strength of the solid electrolyte membrane of the lithium ion battery, so that the prepared all-solid-state lithium ion battery has excellent cycle performance, and is more beneficial to the industrial popularization of the solid battery. Nanoscale Li7La3Zr2O12The electrochemical window of the solid-state electrolyte can also be increased because of Li7La3Zr2O12Has a wide electrochemical window and low electron conductivity, therefore Li7La3Zr2O12The addition of (2) can improve the electrochemical stability of the whole material and the stability of electrolyte to lithium.
Preferably, the lithium salt in the first step is one or more of lithium bistrifluoromethanesulfonylimide, lithium perchlorate, lithium nitrate, lithium difluorooxalato borate and lithium bistrifluorosulfonylimide.
Preferably, the solid electrolyte material in the first step is polyethylene oxide or polypropylene carbonate.
Preferably, the solvent in the first step is acetonitrile, anisole or nitrogen methyl pyrrolidone.
Preferably, the positive electrode material in the positive electrode plate is lithium iron phosphate, and lithium perchlorate is added in the positive electrode plate.
According to the invention, the lithium perchlorate is added into the positive pole piece of the lithium iron phosphate positive pole material, so that lithium ions in the positive pole of the all-solid-state lithium ion battery and lithium ions in the solid electrolyte membrane jointly form a lithium ion battery system with concentration gradient, the conduction speeds of the lithium ions in the positive pole piece, the solid electrolyte membrane and a transition layer formed by the solid electrolyte interface additive of the lithium ion battery are approximately the same, the performance of each material in the battery is favorably exerted, the electrical property of the battery is improved, and the risk of lithium precipitation is reduced.
Preferably, the positive electrode material in the positive electrode plate is a single crystal nickel-cobalt-manganese ternary material, and the lithium niobate is added in the positive electrode plate. In the same way, the lithium niobate is added into the nickel-cobalt-manganese ternary material positive pole piece, so that the lithium ions in the positive pole of the all-solid-state lithium ion battery and the lithium ions in the solid electrolyte membrane jointly form a lithium ion battery system with concentration gradient, the conduction speeds of the lithium ions in the positive pole piece, the solid electrolyte membrane and a transition layer formed by the lithium ion battery solid electrolyte interface additive are approximately the same, the performance of each material in the battery is favorably exerted, the electrical property of the battery is improved, and the risk of lithium precipitation is reduced.
The invention has the beneficial effects that:
the preparation method of the solid electrolyte interface additive of the lithium ion battery controls the reaction process, and the prepared solid electrolyte interface additive of the lithium ion battery has the advantages of less impurities, small impedance and high mechanical strength. The all-solid-state lithium ion battery prepared by the lithium ion battery solid electrolyte interface additive forms an interface with lithium ions having concentration gradient from the positive electrode to the negative electrode, so that the performance of the positive electrode material in the battery can be fully exerted, the interface stability and the stability of the positive electrode material to the lithium negative electrode can be improved, the growth of lithium dendrites is slowed down, and the cycle performance of the battery is improved.
Drawings
Fig. 1 is a graph showing the cycle performance test of the batteries prepared in example 1 and comparative example 1.
Fig. 2 is a graph showing the cycle performance test of the batteries prepared in example 7 and comparative example 2.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
1. Preparing the solid electrolyte interface additive of the lithium ion battery:
the method comprises the following steps: adding a mixture of polyethylene glycol 300 and methyl methacrylate in a mass ratio of 10:5 into a solvent N, N-dimethylformamide for dissolving in an ice-water bath, wherein the mass of solids is 10% of the mass of the solvent, and introducing nitrogen to remove oxygen for 10 min;
step two: adding an initiator azobisisobutyronitrile with the mass of 1 percent of the sum of the mass of the polyethylene glycol 300 and the mass of the methyl methacrylate under the condition of introducing nitrogen, and polymerizing for 24 hours under the condition of oil bath at 65 ℃;
quenching the reaction solution at-10 ℃ to terminate the polymerization;
step three: adding petroleum ether with the volume 3 times of that of the reaction solution, stirring, centrifugally separating the precipitate, washing with ethanol, and drying to obtain the solid electrolyte interface additive of the lithium ion battery.
2. Preparing a solid electrolyte membrane of the lithium ion battery:
dissolving the obtained lithium ion battery solid electrolyte interface additive in dioxolane according to the mass percent of 10%, and adding nano Li 2 times of the mass of the lithium ion battery solid electrolyte interface additive7La3Zr2O12Mixing to obtain solid electrolyte interface additive slurry of the lithium ion battery;
LiClO is added according to the mass ratio of 3:74And polyethylene oxide solutionDissolving in acetonitrile, wherein polyoxyethylene accounts for 8% of the acetonitrile, fully dispersing to prepare slurry, coating the slurry on glassine release paper at 60 ℃, drying, and separating to obtain the solid electrolyte membrane of the lithium ion battery.
Coating the obtained lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained lithium ion battery solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain the modified lithium ion battery solid electrolyte membrane.
1) Ion conductivity testing of modified lithium ion battery solid electrolyte membranes
Testing by adopting an alternating current impedance method: since the normal working temperature of the solid electrolyte membrane of the lithium ion battery prepared by the embodiment is about 60 ℃, the environmental temperature of the test is set to be 60 ℃.
The instrument used was the chenhua electrochemical workstation CHI760 e. The blocking cell was assembled in a glove box before measurement: the modified solid electrolyte membrane obtained in this example was cut into a 16 mm-diameter disk (i.e., SE membrane), which was sandwiched between two stainless steel sheets (i.e., SS) to constitute an SS/SE/SS system for AC impedance testing. The measuring frequency is 0.1Hz to 105Hz. The ionic conductivity σ (S/cm) of the solid electrolyte membrane was calculated as follows:
σ＝l/RS
wherein l, R, S are the thickness (cm), bulk resistance (Ω) and area (cm) of SE film2) The test results are shown in Table 1.
2) Mechanical property test of lithium ion battery solid electrolyte membrane
The modified solid electrolyte membrane of the lithium ion battery prepared in the embodiment is cut into strips with the thickness of 1mm x 20mm, the tensile property test is carried out according to GB/T1040.1-2006 determination of plastic tensile property, a Jinan Tianchen testing machine is used in the test to manufacture a WDW-01G universal tensile machine of a company Limited, the room temperature test is carried out, the gauge length between chucks is 100mm, and the tensile rate is 200 mm.min-1. The test results are shown in Table 1.
3. Preparation of Positive electrode sheet
(1) Fully mixing polyoxyethylene and water according to the mass ratio of 5:100 to obtain viscous binder slurry;
(2) polyoxyethylene and conductive carbon black in a mass ratio: lithium iron phosphate and lithium perchlorate are 1:1: 7.6: 0.4, adding conductive carbon black, lithium iron phosphate and lithium perchlorate into the viscous slurry in batches, fully stirring, adding water to adjust the viscosity to be about 8000mpa.s, and obtaining the anode slurry.
(3) And coating the uniformly stirred anode slurry on an aluminum foil, and drying at 110 ℃ to obtain the anode piece.
4. Preparation of all-solid-state lithium ion battery
And (3) attaching a lithium belt to one surface of the prepared modified solid electrolyte membrane of the lithium ion battery, which is coated with the interface additive slurry, attaching a positive pole piece to the other surface of the modified solid electrolyte membrane of the lithium ion battery, and hot-pressing the positive pole piece in an aluminum plastic membrane at the temperature of 80 ℃ to obtain the all-solid-state lithium ion battery.
5. Test of cycle performance of all-solid-state lithium ion battery
The normal working temperature of the all-solid-state lithium ion battery prepared by the embodiment is about 60 ℃, so the test environment temperature is set to be 60 ℃, the measurement voltage range is 2.2-3.75V, and the charge-discharge current is 0.1C. The cycling curve of the cell is shown in fig. 1, and the cycling performance results are shown in table 1.
Comparative example 1
A lithium ion battery solid electrolyte membrane was prepared in the same manner as in example 1, except that the solid electrolyte membrane of this comparative example was not coated with the lithium ion battery solid electrolyte interface additive slurry.
The ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was carried out in the same manner as in example 1, and the results are shown in table 1. The results in table 1 show that the ion conductivity of the solid electrolyte membrane of the lithium ion battery using the solid electrolyte interface additive of the lithium ion battery of the present invention is significantly increased, which indicates that the solid electrolyte interface additive of the lithium ion battery of the present invention can improve the interface ion conductivity of the solid electrolyte of the lithium ion battery and reduce the interface impedance.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1. As can be seen from the results in table 1, the mechanical strength of the lithium ion battery solid electrolyte membrane using the lithium ion battery solid electrolyte interface additive of the present invention is significantly increased, which indicates that the lithium ion battery solid electrolyte interface additive of the present invention can improve the mechanical strength of the lithium ion battery solid electrolyte membrane.
The positive pole piece is prepared by the same method as the embodiment 1, and is assembled into the all-solid-state lithium ion battery by the lithium ion battery solid electrolyte membrane prepared by the comparative example 1, the battery cycling performance test is carried out by the same method as the embodiment 1, the battery cycling curve is shown in the figure 1, and the cycling performance result is shown in the table 1.
As can be seen from fig. 1, the cycle performance of the battery in example 1 is much better than that of the battery in comparative example 1, and especially the capacity fading of the battery in example 1 is not significant after multiple cycles, while the capacity fading of the battery in comparative example 1 without the addition of the solid electrolyte interface additive of the lithium ion battery of the present invention is significant. As can be seen from the results in table 1, the charge/discharge efficiency of the all-solid-state lithium ion battery prepared using the solid electrolyte of the lithium ion battery solid electrolyte interface additive of the present invention at cycle 50 is greater than that of the all-solid-state lithium ion battery prepared using the solid electrolyte without the lithium ion battery solid electrolyte interface additive of the present invention. Therefore, the all-solid-state lithium ion battery prepared by the method has good cycle performance, and the lithium ion battery solid electrolyte interface additive prepared by the method has high ionic conductivity and high mechanical strength.
Example 2
1. The lithium ion battery solid electrolyte interface additive was prepared in the same manner as in example 1.
2. The lithium ion battery solid electrolyte interface additive slurry is prepared by the same method as the example 1.
LiClO is added according to the mass ratio of 3:74And polyoxyethylene are dissolved in acetonitrile, wherein polyoxyethylene accounts for 5 percent of the mass of the acetonitrile, and nano Li accounting for 60 percent of the mass of the polyoxyethylene is added7La3Zr2O12After fully dispersing to prepare slurryCoating the gel on glassine release paper at 60 ℃, and separating the gel from the glassine release paper after vacuum drying for 12 hours to obtain the solid electrolyte membrane of the lithium ion battery;
coating the obtained lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained lithium ion battery solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain the modified lithium ion battery solid electrolyte membrane.
The ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was carried out in the same manner as in example 1, and the results are shown in table 1.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1.
The positive electrode plate was prepared by the same method as in example 1, and the positive electrode plate and the solid electrolyte membrane of the lithium ion battery prepared in this example were assembled into an all-solid lithium ion battery. The cycle performance test of the all-solid lithium ion battery was performed in the same manner as in example 1, and the cycle performance results of the battery are shown in table 1.
Example 3
1. Preparing the solid electrolyte interface additive of the lithium ion battery:
the method comprises the following steps: adding a mixture of polyethylene glycol 200 and methyl methacrylate in a mass ratio of 10:2 into solvent acetone for dissolving in an ice water bath, wherein the mass of the solid is 10% of that of the solvent, and introducing nitrogen to remove oxygen for 5 min;
step two: adding an initiator azobisisobutyronitrile with the mass of 3 percent of the sum of the mass of the polyethylene glycol 200 and the mass of the methyl methacrylate under the condition of introducing nitrogen, and polymerizing for 24 hours under the condition of oil bath at 65 ℃;
quenching the reaction solution at-10 ℃ to terminate the polymerization;
step three: adding petroleum ether with the volume 3 times of that of the reaction solution, stirring, centrifugally separating the precipitate, washing with ethanol, and drying to obtain the solid electrolyte interface additive of the lithium ion battery.
2. Preparing a solid electrolyte membrane of the lithium ion battery:
the lithium ion battery solid electrolyte interface additive slurry is prepared by the same method as the example 1.
Dissolving lithium bistrifluoromethanesulfonimide and polypropylene carbonate in an anisole according to a mass ratio of 1:9, wherein the polypropylene carbonate accounts for 8% of the mass of the anisole, fully dispersing to prepare slurry, coating the slurry on glassine release paper at 130 ℃, drying, and separating to obtain the solid electrolyte membrane of the lithium ion battery.
Coating the obtained lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained lithium ion battery solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain the modified lithium ion battery solid electrolyte membrane.
Since the normal operating temperature of the solid electrolyte membrane of the lithium ion battery manufactured in this example was about 25 ℃, the ambient temperature for the test was set to 25 ℃, and the ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was performed in the same manner as in example 1 in the other steps, and the results are shown in table 1.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1.
The positive electrode plate is prepared by the same method as that of the embodiment 1, and the positive electrode plate and the lithium ion battery solid electrolyte membrane prepared in the embodiment are assembled into the all-solid-state lithium ion battery, and the cycle performance test of the all-solid-state lithium ion battery is carried out. Since the normal operating temperature of the all-solid-state lithium ion battery prepared in this example was about 25 ℃, the ambient temperature of the test was set to 25 ℃, the cycle performance of the battery was tested in the same manner as in example 1, and the results are shown in table 1.
Example 4
1. The lithium ion battery solid electrolyte interface additive was prepared in the same manner as in example 1.
2. The lithium ion battery solid electrolyte interface additive slurry is prepared by the same method as the example 1.
Dissolving lithium salt (wherein the mass ratio of lithium bistrifluoromethanesulfonimide to lithium nitrate is 10: 1) and polyoxyethylene in azomethylpyrrolidone according to the mass ratio of 3:1, wherein the polyoxyethylene accounts for the azomethylpyrrolidone8 percent of the weight of the polyethylene oxide, and nano Li accounting for 90 percent of the mass of the polyethylene oxide7La3Zr2O12Fully dispersing to prepare slurry, coating the slurry on glassine release paper at 60 ℃, drying the glassine release paper in vacuum at 60 ℃ for 12 hours, and separating to obtain the solid electrolyte membrane of the lithium ion battery;
and coating the obtained lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain the modified lithium ion battery solid electrolyte membrane.
The ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was carried out in the same manner as in example 1, and the results are shown in table 1.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1.
The positive electrode plate was prepared by the same method as in example 1, and the positive electrode plate and the solid electrolyte membrane of the lithium ion battery prepared in this example were assembled into an all-solid lithium ion battery. The cycle performance test of the all-solid lithium ion battery was performed in the same manner as in example 1, and the cycle performance results of the battery are shown in table 1.
Example 5
1. The lithium ion battery solid electrolyte interface additive was prepared in the same manner as in example 1.
2. Preparing a solid electrolyte membrane of the lithium ion battery:
the lithium ion battery solid electrolyte interface additive slurry is prepared by the same method as the example 2.
Dissolving lithium salt (wherein the mass ratio of lithium difluorooxalate borate to lithium bistrifluoromethanesulfonylimide is 10: 1) and polyoxyethylene in the azomethicone at a mass ratio of 3:8, wherein the polyoxyethylene accounts for 8% of the mass of the azomethicone, fully dispersing the mixture to prepare slurry, coating the slurry on glassine release paper at 60 ℃, drying the slurry in vacuum at 150 ℃ for 12 hours, and separating the slurry to obtain the solid electrolyte membrane of the lithium ion battery;
coating the obtained lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained lithium ion battery solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain the modified lithium ion battery solid electrolyte membrane.
The ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was carried out in the same manner as in example 1, and the results are shown in Table 1.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1.
The positive electrode plate was prepared by the same method as in example 1, and the positive electrode plate and the solid electrolyte membrane of the lithium ion battery prepared in this example were assembled into an all-solid lithium ion battery. The cycle performance test of the all-solid lithium ion battery was performed in the same manner as in example 1, and the cycle performance results of the battery are shown in table 1.
Example 6
1. The lithium ion battery solid electrolyte interface additive was prepared in the same manner as in example 5.
2. Preparation of solid electrolyte membrane of lithium ion battery
The lithium ion battery solid electrolyte interface additive slurry is prepared by the same method as the example 2.
Dissolving lithium salt (wherein the mass ratio of lithium difluorooxalato borate to lithium perchlorate is 10: 1) and polyoxyethylene in the azomethylpyrrolidone according to the mass ratio of 3:8, wherein the polyoxyethylene accounts for 8% of the mass of the azomethylpyrrolidone, and Li with the particle size of 100 nanometers and accounts for 90% of the mass of the polyoxyethylene is added7La3Zr2O12Fully dispersing to prepare slurry, coating the slurry on glassine release paper at 60 ℃, drying the glassine release paper in vacuum at 60 ℃ for 12 hours, and separating to obtain the solid electrolyte membrane of the lithium ion battery;
coating the obtained lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained lithium ion battery solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain the modified lithium ion battery solid electrolyte membrane.
The ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was carried out in the same manner as in example 1, and the results are shown in table 1.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1.
The positive electrode plate was prepared by the same method as in example 1, and the positive electrode plate and the solid electrolyte membrane of the lithium ion battery prepared in this example were assembled into an all-solid lithium ion battery. The cycle performance test of the all-solid lithium ion battery was performed in the same manner as in example 1, and the cycle performance results of the battery are shown in table 1.
Example 7
1. The lithium ion battery solid electrolyte interface additive was prepared in the same manner as in example 1.
2. A lithium ion battery solid electrolyte membrane was prepared in the same manner as in example 1.
The ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was carried out in the same manner as in example 1, and the results are shown in table 1.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1.
3. Preparation of Positive electrode sheet
(1) Fully mixing polyoxyethylene and N-methyl pyrrolidone according to the mass ratio of 5:100 to obtain viscous binder slurry;
(2) polyoxyethylene and conductive carbon black in a mass ratio: single crystal LiNi0.5Co0.2Mn0.3O2Lithium niobate is 1:1: 7.6: 0.4 to the above viscous slurry was added conductive carbon black, single crystal LiNi in divided portions0.5Co0.2Mn0.3O2And lithium niobate, fully stirring, and adding N-methyl pyrrolidone to adjust the viscosity to be about 8000mpa.s, thereby obtaining the anode slurry.
(3) And coating the uniformly stirred anode slurry on an aluminum foil, and drying at 110 ℃ to obtain the anode piece.
4. Preparation of all-solid-state lithium ion battery
And (3) attaching a lithium belt to one surface of the prepared modified solid electrolyte membrane of the lithium ion battery, which is coated with the interface additive slurry, attaching a positive pole piece to the other surface of the modified solid electrolyte membrane of the lithium ion battery, and hot-pressing the positive pole piece in an aluminum plastic membrane at 150 ℃ to obtain the all-solid-state lithium ion battery.
5. Test of cycle performance of all-solid-state lithium ion battery
Since the normal operating temperature of the all-solid-state lithium ion battery prepared in this example is about 60 ℃, the obtained all-solid-state lithium ion battery is measured in an environment of 60 ℃, the measurement voltage range is 3-4.2V, and the charge and discharge current is 0.1C. The cycling profile of the cell is shown in fig. 2, and the cycling performance results are shown in table 1.
Example 8
1. The lithium ion battery solid electrolyte interface additive was prepared in the same manner as in example 1.
2. Preparation of solid electrolyte membrane of lithium ion battery
The lithium ion battery solid electrolyte interface additive slurry is prepared by the same method as the example 2.
Dissolving lithium salt (wherein the mass ratio of the lithium bistrifluoromethanesulfonylimide to the lithium bisfluorosulfonylimide is 10: 1) and polyoxyethylene in a mass ratio of 3:2 in azomethylpyrrolidone, wherein the polyoxyethylene accounts for 8% of the mass of the azomethylpyrrolidone, and Li with the particle size of 100 nanometers and accounts for 90% of the mass of the polyoxyethylene is added7La3Zr2O12Fully dispersing to prepare slurry, coating the slurry on glassine release paper at 60 ℃, drying the glassine release paper in vacuum at 60 ℃ for 12 hours, and separating to obtain the solid electrolyte membrane of the lithium ion battery;
coating the obtained lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained lithium ion battery solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain the modified lithium ion battery solid electrolyte membrane.
The ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was carried out in the same manner as in example 1, and the results are shown in table 1.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1.
The positive electrode plate was prepared in the same manner as in example 7, and an all-solid-state lithium ion battery was prepared using this positive electrode plate and the solid electrolyte membrane of the lithium ion battery prepared in this example. The cycle performance test of the all-solid lithium ion battery was performed in the same manner as in example 1, and the cycle performance results of the battery are shown in table 1.
Comparative example 2
A lithium ion battery solid electrolyte membrane was prepared in the same manner as in example 7, except that the solid electrolyte membrane of this comparative example was not coated with the lithium ion battery solid electrolyte interface additive slurry.
The ionic conductivity test of the solid electrolyte membrane of the lithium ion battery was carried out in the same manner as in example 1, and the results are shown in table 1.
Mechanical properties of the lithium ion battery solid electrolyte membrane were measured in the same manner as in example 1, and the results are shown in table 1.
A positive electrode plate was prepared in the same manner as in example 7, and was assembled with the lithium ion battery solid electrolyte membrane prepared in this comparative example 1 to form an all-solid lithium ion battery. And the cycle performance test of the all solid-state lithium ion battery was carried out in the same manner as in example 7, the cycle curve of the battery is shown in fig. 2, and the cycle performance results are shown in table 1.
As can be seen from fig. 2, the cycle performance of the battery in example 7 is much better than that of the battery in comparative example 2, especially after the battery is cycled for multiple times, the capacity of example 7 added with the lithium ion battery solid electrolyte interface additive of the present invention does not decay after 30 charge and discharge cycles, and the capacity exerts a gradual rise, indicating that the battery is further activated; in contrast to comparative example 2, in which the lithium ion battery solid electrolyte interface additive of the present invention was not added, the capacity gradually decreased from the start of the cycle. This indicates that, for single crystal LiNi0.5Co0.2Mn0.3O2For the anode material, the use of the solid electrolyte interface additive of the lithium ion battery obviously improves the cycle performance of the all-solid-state lithium ion battery.
TABLE 1
From the above results, it can be seen that:
the preparation method of the solid electrolyte interface additive of the lithium ion battery controls the reaction process, so that the prepared solid electrolyte interface additive of the lithium ion battery has less impurities, small impedance and high mechanical strength. The all-solid-state lithium ion battery prepared by the application method of the lithium ion battery solid electrolyte interface additive has good cycle performance. The lithium ion battery prepared by the lithium ion battery solid electrolyte interface additive can be used for preparing lithium ion gradient interfaces with different concentrations from the positive electrode to the negative electrode, so that the performance of the positive electrode material can be fully exerted, the interface stability can be improved, the stability of the lithium negative electrode can be improved, the growth of lithium dendrites can be relieved, and the cycle performance of the battery can be improved.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features related to the embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. The above embodiments are only some embodiments of the present invention, not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention. For example, in the present invention, for the dissolution of polyethylene glycol and methyl methacrylate, N-dimethylformamide or acetone is used as a solvent, and other solvents as long as both of them can be dissolved can be used; for the polymerization reaction of polyethylene glycol and methyl methacrylate, the initiator azobisisobutyronitrile is used in the invention, and the polymerization reaction is polymerized for 24 hours under the condition of oil bath at 60 ℃; one of ordinary skill in the art can also select other free radical initiators to initiate the polymerization reaction and select the appropriate reaction temperature and time based on the characteristics of the different initiators. For another example, the present specification only shows the use of a solid electrolyte membrane made of the lithium ion battery solid electrolyte interface additive of the present invention, a positive electrode material lithium iron phosphate, and a positive electrode material nickel-cobalt-manganese ternary coordination to manufacture a battery, and the lithium ion battery solid electrolyte interface additive of the present invention is coated on the surface of the lithium ion battery solid electrolyte because the wettability between the solid electrolyte and the metal lithium in the battery is improved, the battery interface impedance is reduced, and the mechanical strength of the solid electrolyte membrane is improved, thereby improving the capacity and cycle performance of the all-solid-state lithium ion battery. Therefore, the lithium ion battery solid electrolyte interface additive can also be prepared into a solid electrolyte membrane to be matched with other cathode materials, and can also improve the capacity and the cycle performance of the all-solid-state lithium ion battery, and the details are not repeated herein.
Claims (10)
1. The preparation method of the solid electrolyte interface additive of the lithium ion battery is characterized by comprising the following steps:
the method comprises the following steps: under the ice-water bath, adding a mixture of polyethylene glycol with the molecular weight not more than 300 and methyl methacrylate into N, N-dimethylformamide or acetone for dissolving, and introducing nitrogen to remove oxygen for 5-10 min;
step two: under the condition of introducing nitrogen, adding an initiator accounting for 1-3% of the mass sum of the polyethylene glycol and the methyl methacrylate for polymerization reaction, and quenching the reaction solution to terminate the polymerization after the reaction is completed;
step three: adding petroleum ether, stirring, separating the precipitate, washing with ethanol, and drying to obtain the solid electrolyte interface additive for lithium ion battery.
2. The preparation method of the solid electrolyte interface additive for the lithium ion battery according to claim 1, wherein the mass ratio of the polyethylene glycol to the methyl methacrylate is 10: 2-5.
3. The application of the lithium ion battery solid electrolyte interface additive prepared by the method of claim 1 or 2, which comprises the following steps:
the method comprises the following steps: dissolving the lithium ion battery solid electrolyte interface additive in dioxolane, wherein the lithium ionsThe mass of the solid electrolyte interface additive of the sub-battery is 10% of that of the dioxolane; adding nano Li 2 times of the mass of the solid electrolyte interface additive of the lithium ion battery7La3Zr2O12Mixing to obtain solid electrolyte interface additive slurry of the lithium ion battery;
mixing lithium salt and a solid electrolyte material according to the mass ratio of 1-6: 9-4, adding the mixture into a solvent, dispersing the mixture to prepare slurry, coating the slurry on glassine release paper at the temperature of 60-130 ℃, drying the slurry, and separating the dried product to obtain a lithium ion battery solid electrolyte membrane;
coating the prepared lithium ion battery solid electrolyte interface additive slurry on one surface of the obtained lithium ion battery solid electrolyte membrane, wherein the coating thickness is not more than 5 mu m, and drying to obtain a modified lithium ion battery solid electrolyte membrane;
step two: preparing a positive pole piece;
and (3) attaching a lithium belt to one surface of the prepared modified lithium ion battery solid electrolyte membrane, which is coated with the lithium ion battery solid electrolyte interface additive slurry, attaching a positive pole piece to the other surface of the modified lithium ion battery solid electrolyte membrane, and hot-pressing the positive pole piece in an aluminum plastic membrane at the temperature of 80-150 ℃ to obtain the all-solid-state lithium ion battery.
4. The application of the lithium ion battery solid electrolyte interface additive according to claim 3, wherein the lithium ion battery solid electrolyte membrane in the first step is further added with nanoscale Li7La3Zr2O12。
5. The use of the lithium ion battery solid electrolyte interface additive of claim 4, wherein the nanoscale Li is7La3Zr2O12The mass of the solid electrolyte material is 60-90% of the mass of the solid electrolyte material.
6. The use of the solid electrolyte interface additive for lithium ion batteries according to claim 5, wherein the lithium salt in the first step is one or more of lithium bistrifluoromethanesulfonylimide, lithium perchlorate, lithium nitrate, lithium difluorooxalato borate and lithium bistrifluorosulfonylimide.
7. The use of the solid electrolyte interface additive for lithium ion batteries according to claim 5, wherein the solid electrolyte material in the first step is polyethylene oxide or polypropylene carbonate.
8. The use of the solid electrolyte interface additive for lithium ion batteries according to claim 5, wherein the solvent in the first step is acetonitrile, anisole or azomethylpyrrolidone.
9. The application of the solid electrolyte interface additive for the lithium ion battery as claimed in claim 5, wherein the positive electrode material in the positive electrode plate is lithium iron phosphate, and lithium perchlorate is added in the positive electrode plate.
10. The application of the lithium ion battery solid electrolyte interface additive according to claim 5, wherein the positive electrode material in the positive electrode plate is a single crystal nickel-cobalt-manganese ternary material, and lithium niobate is added in the positive electrode plate.
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Application publication date: 20200602 |