CN112687960A - Method for stabilizing solid electrolyte/metal negative electrode interface by using zinc salt - Google Patents
Method for stabilizing solid electrolyte/metal negative electrode interface by using zinc salt Download PDFInfo
- Publication number
- CN112687960A CN112687960A CN202011577323.9A CN202011577323A CN112687960A CN 112687960 A CN112687960 A CN 112687960A CN 202011577323 A CN202011577323 A CN 202011577323A CN 112687960 A CN112687960 A CN 112687960A
- Authority
- CN
- China
- Prior art keywords
- polymer electrolyte
- salt
- metal
- solid
- electrolyte layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 83
- 239000002184 metal Substances 0.000 title claims abstract description 83
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 10
- 150000003751 zinc Chemical class 0.000 title claims abstract description 9
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 121
- 239000003792 electrolyte Substances 0.000 claims abstract description 94
- 239000011701 zinc Substances 0.000 claims abstract description 68
- 150000003839 salts Chemical class 0.000 claims abstract description 62
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 36
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 239000005823 Propineb Substances 0.000 claims abstract description 8
- KKMLIVYBGSAJPM-UHFFFAOYSA-L propineb Chemical compound [Zn+2].[S-]C(=S)NC(C)CNC([S-])=S KKMLIVYBGSAJPM-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims abstract description 3
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 75
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- 229910052744 lithium Inorganic materials 0.000 claims description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 30
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 19
- -1 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 18
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 229910010941 LiFSI Inorganic materials 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 10
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical group [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 claims description 10
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical group [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910020892 NaBOB Inorganic materials 0.000 claims description 2
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 claims description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 description 29
- 239000012528 membrane Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910010710 LiFePO Inorganic materials 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 150000002641 lithium Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- ZDHURYWHEBEGHO-UHFFFAOYSA-N potassiopotassium Chemical compound [K].[K] ZDHURYWHEBEGHO-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A method of stabilizing a solid electrolyte/metal anode interface with a zinc salt, the method comprising the steps of: (1) preparing a polymer electrolyte layer; (2) adding Zn salt in the preparation process of the polymer electrolyte, and drying with a solvent to obtain the Zn salt modified polymer electrolyte, wherein the mass content of the Zn salt is controlled to be 0.1-3%; (3) compounding the Zn salt modified polymer electrolyte prepared in the step (2) on the surface of the polymer electrolyte layer prepared in the step (1) to form a composite electrolyte layer, and assembling a solid-state metal battery by taking the composite electrolyte layer as a solid-state electrolyte, wherein the Zn salt modified polymer electrolyte is positioned between the polymer electrolyte layer and a metal electrode; the Zn salt is selected from one or more of zinc trifluoromethanesulfonate, zinc perchlorate, propineb, zinc dimethacrylate, zinc trifluoromethanesulfonylimide and zinc stearate. The method of the invention can lead the solid-state metal battery to show high capacity, ultra-long cycle life and cycle stability.
Description
(I) technical field
The invention belongs to the field of solid batteries, and relates to a method for stabilizing a solid electrolyte/metal cathode interface by using zinc salt.
(II) background of the invention
The solid-state metal battery refers to a secondary battery system consisting of a solid electrolyte and a metal negative electrode, and the interface between the metal negative electrode and the polymer electrolyte is also important for prolonging the cycle life of the solid-state metal battery by removing the optimization and improvement of the ionic conductivity and the mechanical property of the solid electrolyte, particularly the polymer electrolyte. However, there are still problems with the polymer electrolyte/metal negative electrode interface: firstly, the metal is in contact with the interface of the polymer electrolyte, and the polymer electrolyte is difficult to wet the surface of the metal cathode, so that the actual contact area between the metal and the polymer electrolyte is limited, and the solid-solid contact capacity is far smaller than the solid-liquid contact capacity, thereby causing larger interface impedance; secondly, the interfacial stress between the polymer electrolyte and the electrode material and the volume change of metal in the charge-discharge process can generate stress on the interface, so that the solid-solid interface contact is deteriorated, and the internal resistance of the battery is increased; thirdly, the interface stability of the polymer electrolyte to the metal, and the chemical/electrochemical potential difference between the polymer electrolyte and the metal easily cause the diffusion of interface elements, and a passivation film covering the surface of the metal cathode is formed on the interface. The thickness of the passivation film is continuously increased along with the time, the interface impedance is increased, the capacity of the battery is reduced, the cycle performance is reduced, and the current distribution is not uniform in the metal deposition-dissolution process, so that the performance is influenced. Thus, the safety and energy density of the battery are limited, and the large-scale application of the solid-state lithium battery is limited. Multiple means such as metal negative electrode surface modification, polymer electrolyte optimization and the like can be used for stabilizing the interface of the polymer electrolyte/the metal negative electrode.
Disclosure of the invention
The invention aims to provide a method for stabilizing a solid electrolyte/metal negative electrode interface by using a zinc salt, which enables the interface to show good compatibility by a method of physically inhibiting and chemically changing components, and finally enables a solid metal battery to show high capacity, ultra-long cycle life and cycle stability.
The following specifically describes the technical means of the present invention.
The invention provides a method for stabilizing a solid electrolyte/metal negative electrode interface by using zinc salt, which comprises the following steps:
(1) preparing a polymer electrolyte layer;
(2) adding Zn salt in the preparation process of the polymer electrolyte, and drying with a solvent to obtain the Zn salt modified polymer electrolyte, wherein the mass content of the Zn salt is controlled to be 0.1-3%;
(3) compounding the Zn salt modified polymer electrolyte prepared in the step (2) on the surface of the polymer electrolyte layer prepared in the step (1) to form a composite electrolyte layer, and assembling a solid-state metal battery by taking the composite electrolyte layer as a solid-state electrolyte, wherein the Zn salt modified polymer electrolyte is positioned between the polymer electrolyte layer and a metal electrode;
the Zn salt is selected from one or more of zinc trifluoromethanesulfonate, zinc perchlorate, propineb, zinc dimethacrylate, zinc trifluoromethanesulfonylimide and zinc stearate.
Preferably, the polymer electrolyte layer has a thickness of 70 to 100 μm.
Preferably, the film thickness of the Zn salt modified polymer electrolyte is less than 20 microns, and more preferably 10-15 microns.
In steps (1) and (2), the polymer electrolyte is suitable for solid metal batteries, and according to the classification of solid metal batteries, namely solid metal lithium batteries, solid metal sodium batteries and solid metal potassium batteries, the polymer electrolyte is composed of a polymer and a corresponding conductive metal salt, wherein the metal salt refers to a conductive lithium salt or a conductive sodium salt or a conductive potassium salt, the mass ratio of the polymer to the conductive metal salt is usually 5:1-20:1, the polymer can be one or a combination of more than two of polyethylene oxide (PEO), Polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF), and the conductive lithium salt can be one or a combination of more than two of polyethylene oxide (PEO), Polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF)LiTFSI、LiFSI、LiClO4One or more of LiBOB and LiDFOB, and the conductive sodium salt can be NaTFSI, NaFSI and NaClO4One or more of NaBOB and NaDFOB, and the conductive potassium salt can be KTFSI, KFSI and KClO4One or a combination of more than two of KBOB and KDFOB. The preparation method of the polymer electrolyte layer is generally as follows: and (2) dissolving the polymer and the conductive metal salt together in acetonitrile, N-dimethylformamide, N-methylpyrrolidone, acetone or methanol solvent to obtain a mixed solution, placing the mixed solution in a polytetrafluoroethylene mold, and volatilizing the solvent to obtain the polymer electrolyte layer. The preparation method of the Zn salt modified polymer electrolyte comprises the following steps: and (2) dissolving the polymer, the conductive metal salt and the Zn salt into acetonitrile, N-dimethylformamide, N-methylpyrrolidone, acetone or methanol to obtain a mixed solution, placing the mixed solution into a polytetrafluoroethylene mold, and volatilizing the solvent to obtain the Zn salt modified polymer electrolyte. The solvent can be volatilized naturally for more than 12 hours in a drying room with the dew point temperature of-60 ℃ at room temperature or for more than 6 hours by heating and evaporating the solvent by using a heating table.
In the step (2) of the present invention, the preferable mass content of the Zn salt in the Zn salt-modified polymer electrolyte is 0.5%.
In step (3) of the present invention, the Zn salt modified polymer electrolyte prepared in step (2) is preferably compounded on the surface of the polymer electrolyte layer prepared in step (1) to form a composite electrolyte layer by one of the following two ways:
independently forming a film by using a polymer electrolyte modified by Zn salt, then pasting the film on the surface of the polymer electrolyte layer prepared in the step (1), and standing for more than 1h at the temperature of 60-80 ℃;
preparing the Zn salt modified polymer electrolyte prepared in the step (2) into dispersion liquid, then pouring the dispersion liquid onto the surface of the polymer electrolyte layer prepared in the step (1), and volatilizing the solvent to form a film layer.
It is particularly noted that when assembling the half cell, the polymer electrolyte modified with Zn salt is compounded on both surfaces of the polymer electrolyte layer; when the full battery is assembled, only one side surface of the polymer electrolyte layer is required to be compounded with the polymer electrolyte modified by the Zn salt.
In step (3) of the present invention, the positive electrode may be LiNi1/3Co1/3Mn1/3O2(NCM111)、NCM811、NCM523、LiFePO4And the metal negative electrode can be metal lithium, metal sodium, metal potassium and the like, lithium (sodium, potassium)/electrolyte/lithium (sodium, potassium) half-cells are assembled, metal stability is tested, and positive electrode/electrolyte/metal negative electrode full-cells are assembled, and cycle stability is tested.
The invention needs to control the environmental water content to be less than 1ppm in the preparation of the polymer electrolyte and the assembly process of the battery.
Compared with the prior art, the invention has the following beneficial effects: modification of Zn salt can strengthen the mechanical performance of electrolyte and physically inhibit the growth of metal dendrite; on the other hand, the conductivity and stability of the interfacial metal are increased by chemical reaction with the metal negative electrode. Finally, the assembled solid metal battery has high capacity, long service life and good cycling stability.
(IV) description of the drawings
Fig. 1 shows the performance of lithium-lithium batteries assembled by the bis (trifluoromethanesulfonic acid) zinc modified lithium sheet or unmodified lithium sheet prepared in example 1 and PAN-LiFSI electrolyte.
FIG. 2 shows a lithium sheet modified with zinc bistrifluoromethanesulfonate or an unmodified lithium sheet and LiFePO prepared in example 14Full cell performance of the anode, PAN-LiFSI electrolyte assembly.
Fig. 3 is a nano-indentation test curve of zinc bistrifluoromethanesulfonate-modified multi-layer composite electrolyte prepared in example 1 and an unmodified electrolyte prepared in comparative example 1 after electrochemical cycling.
Fig. 4 is a graph showing the performance of lithium-lithium batteries assembled by the zinc dimethacrylate-modified lithium sheet or the unmodified lithium sheet and the PEO-liddob electrolyte prepared in example 2.
Fig. 5 is a graph showing the performance of lithium-lithium batteries assembled by the zincazium-propionate modified lithium sheet or unmodified lithium sheet prepared in example 5 and PAN-LiTFSI electrolyte.
(V) detailed description of the preferred embodiment
The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Dissolving 0.53g of PAN and 0.187g of LiFSI together in 10ml of N, N-dimethylformamide solvent, stirring at 80 ℃ for more than 24h, adding 0.5 wt% of zinc bistrifluoromethane sulfonate when stirring for 10h to modify PAN-LiFSI electrolyte, uniformly mixing, placing in a polytetrafluoroethylene mold, and independently forming a film after the N, N-dimethylformamide solvent is volatilized to obtain the Zn salt modified polymer electrolyte film, wherein the film thickness is 10 microns.
By adopting the similar method, PAN and LiFSI electrolyte (the mass ratio is 530:187) without zinc bistrifluoromethane sulfonate are dissolved in N, N-dimethylformamide solvent together, then the mixture is placed in a polytetrafluoroethylene mold, and when the N, N-dimethylformamide solvent is volatilized, a film is formed independently, and the thickness of an electrolyte film layer is controlled to be 70-75 micrometers, so that the PAN-LiFSI polymer electrolyte layer is obtained.
And compounding a polymer electrolyte membrane modified by Zn salt on the two side surfaces of the PAN-LiFSI polymer electrolyte layer, standing for 2 hours at 60 ℃ to obtain a composite electrolyte layer 1, and taking the composite electrolyte layer as a solid electrolyte to assemble a metal lithium/solid electrolyte/metal lithium half-battery, which is marked as a metal lithium half-battery I.
Compounding a polymer electrolyte membrane modified by Zn salt on the single-side surface of the PAN-LiFSI polymer electrolyte layer, standing for 2 hours at 60 ℃ to obtain a compound electrolyte layer 2, taking the compound electrolyte layer as a solid electrolyte, enabling the polymer electrolyte membrane modified by Zn salt to be close to a metal lithium cathode, and adopting LiFePO as an anode4And (3) assembling an active material, namely assembling a positive electrode/solid electrolyte/lithium metal negative electrode all-solid-state battery, marking as a lithium metal all-solid battery I, and testing the cycle performance of the lithium metal all-solid-state battery I at 50 ℃.
The water content is controlled to be less than 1ppm in the whole preparation process.
Comparative example 1
Referring to example 1, PAN and LiFSI electrolytes (mass ratio 530:187) not containing zinc bistrifluoromethane sulfonate were dissolved together in N, N-dimethylformamide solvent, and then placed in a polytetrafluoroethylene mold, and the N, N-dimethylformamide solvent was volatilized to form a film alone, and the thickness of the electrolyte was controlled to 90 to 95 μm, to obtain a polymer electrolyte layer 1. A lithium metal/solid electrolyte/lithium metal half cell, denoted as lithium metal half cell I', was assembled as in example 1, replacing the composite electrolyte layer 1 in example 1 with a polymer electrolyte layer 1.
Referring to example 1, PAN and LiFSI electrolytes (mass ratio 530:187) not containing zinc bistrifluoromethane sulfonate were dissolved together in N, N-dimethylformamide solvent, and then the N, N-dimethylformamide solvent was volatilized to form a film alone, and the thickness of the electrolyte was controlled to 80 to 85 μm, to obtain a polymer electrolyte layer 2. A positive electrode/solid electrolyte/lithium metal negative electrode all-solid-state battery, designated as a lithium metal all-solid battery I', was assembled in the same manner as in example 1, except that the composite electrolyte layer 2 in example 1 was replaced with the polymer electrolyte layer 2, and the cycle performance at 50 ℃ thereof was tested.
FIG. 1 shows the stability of the PAN-LiFSI electrolytes prepared in example 1 and comparative example 1 with or without zinc bistrifluoromethanesulfonate modification to metallic lithium at 50 ℃ at a current density of 0.1mA cm-2Capacity of 0.1mAh cm-2The metal lithium half-cells I and I 'are tested under the condition, and as can be seen from the figure, the metal lithium half-cell I' without the electrolyte assembly modified by Zn can only stably circulate for 400h, and the polarization voltage is 100mV, and the cycle life of the lithium-lithium cell can be doubled by modifying the zinc bistrifluoromethane sulfonate, and the polarization voltage is reduced to about 65 mV. The positive effect of Zn salt in stabilizing the interface between PAN-LiFSI electrolyte and metallic lithium can be seen.
FIG. 2 is a graph showing the cycle performance at 50 ℃ of full cells I and I 'prepared in example 1 and comparative example 1, with or without zinc bistrifluoromethane sulfonate, and the charge and discharge tests were performed on the full cells I and I' at a current density of 0.3C and a voltage range of 2.5-3.8V. Without the modification of Zn salt, the reduction of the coulombic efficiency occurs after the full cell I' circulates for 20 circles, and the coulombic efficiency fluctuates greatly along with the increase of the circulation, which indicates that the side reaction of the interface is intensified.The modification of Zn salt can lead the full battery I to stably circulate for more than 80 circles, the coulombic efficiency is close to 100 percent, and the circulating capacity is 145mAh g-1。
Fig. 3 is a nanoindentation test of the composite electrolyte layer 2 and the polymer electrolyte layer 2 prepared in example 1 and comparative example 1 after 50 electrochemical cycles. As can be seen from the test results, the polymer electrolyte layer 2 of comparative example 1, after electrochemical cycling, had a modulus (side near lithium) of 200 MPa; the modulus of the electrolyte compounded by the zinc salt can be improved to 400MPa, which shows that the modification of the zinc salt can improve the mechanical property of the composite electrolyte.
Example 2
0.44g of PEO and 0.180g of LiDFOB are jointly dissolved in 15ml of acetonitrile, stirred for more than 24h at the temperature of 30 ℃, zinc dimethacrylate (the mass amount of the zinc dimethacrylate accounts for 1 wt% of the total mass of the PEO and the LiDFOB) is added while stirring for 10h, and a dispersion liquid is obtained after uniform mixing and is used for modifying PEO-LiDFOB electrolyte.
Dissolving PEO and LiDFOB electrolyte (mass ratio 44:18) which do not contain zinc dimethacrylate into acetonitrile solvent, then placing the mixture into a polytetrafluoroethylene mold, and independently forming a film when the acetonitrile solvent is volatilized, wherein the thickness is controlled to be 70-75 micrometers, so as to obtain the PEO-LiDFOB polymer electrolyte layer.
Respectively pouring dispersion liquid containing 1 wt% of zinc dimethacrylate on two sides of the PEO-LiDFOB polymer electrolyte layer, and volatilizing an acetonitrile solvent to enable electrolyte modified by 1 wt% of zinc dimethacrylate to form a film on the surface of the PEO-LiDFOB polymer electrolyte layer, wherein the film thickness of the two sides is 5 micrometers respectively, so as to obtain the composite electrolyte layer 1. The lithium-lithium half cell was assembled as a solid electrolyte and designated as metal lithium half cell II.
Compounding a 1 wt% zinc dimethacrylate modified polymer electrolyte membrane on the single-side surface of the PEO-LiDFOB polymer electrolyte layer according to the method, wherein the membrane thickness is 5 microns to obtain a composite electrolyte layer 2, taking the composite electrolyte layer as a solid electrolyte, enabling the 1 wt% zinc dimethacrylate modified polymer electrolyte membrane to be close to a metal lithium negative electrode, assembling a positive electrode/solid electrolyte/metal lithium negative electrode all-solid-state battery by adopting an NCM111 active material as a positive electrode, marking as a metal lithium all-solid-state battery II, and testing the cycle performance of the metal lithium all-solid-state battery II at 50 ℃.
The water content is controlled to be less than 1ppm in the whole process.
Comparative example 2
Referring to example 2, PEO and liddob electrolyte (mass ratio 44:18) not containing zinc dimethacrylate were collectively dissolved in acetonitrile solvent, and then separately formed into a film while the acetonitrile solvent was volatilized, and the thickness of the electrolyte was controlled to 80 to 85 μm, to obtain a polymer electrolyte layer 1. The composite electrolyte layer 1 of example 2 was replaced with the polymer electrolyte layer 1, and a lithium metal/solid electrolyte/lithium metal half cell, denoted as lithium metal half cell II', was assembled as in example 2.
Referring to example 2, PEO and liddob electrolyte (mass ratio 44:18) not containing zinc dimethacrylate were collectively dissolved in acetonitrile solvent, and then film-formed separately by volatilizing the solvent, with the thickness of the electrolyte being controlled to 75 to 80 μm, to obtain a polymer electrolyte layer 2. The composite electrolyte layer 2 of example 2 was replaced with the polymer electrolyte layer 2, and a positive electrode/solid electrolyte/lithium metal full cell, designated as lithium metal full cell II', was assembled according to the method of example 2 and tested for 50 ℃ cycle performance.
FIG. 4 shows the stability of the PEO-LiDFOB electrolytes prepared in example 2 and comparative example 2 with or without zinc dimethacrylate modification to lithium metal at 50 ℃ at a current density of 0.1mA cm-2Capacity of 0.1mAh cm-2The metal lithium half-batteries II and II 'are tested under the condition, and as can be seen from the figure, the metal lithium half-battery II' without the electrolyte assembly modified by Zn salt can only be stably circulated for 250h, and the cycle life of the lithium-lithium battery can be prolonged by nearly one time by modifying zinc dimethacrylate, and the stable circulation is more than 440 h. The positive effect of the Zn salt in stabilizing the interface between the PEO-LiDFOB electrolyte and the lithium metal can be seen.
Example 3
0.64g of PVDF and 0.296g of NaTFSI are jointly dissolved in 15ml of N, N-dimethylformamide, stirred for more than 24h at 50 ℃, and added with zinc trifluoromethanesulfonylimide (the mass amount of the zinc trifluoromethanesulfonylimide is 0.25 wt% of the total mass of the PVDF and the NaTFSI) while stirred for 10h, and the mixture is uniformly mixed to obtain a dispersion liquid which is used for modifying the PVDF-NaTFSI electrolyte.
And (2) dissolving PVDF and NaTFSI (the mass ratio of PVDF to NaTFSI is 640:296) into N, N-dimethylformamide together, then placing the obtained solution into a polytetrafluoroethylene mold, and independently forming a film when the N, N-dimethylformamide solvent is volatilized, wherein the thickness needs to be controlled to be 80-100 micrometers, so as to obtain the PVDF-NaTFSI polymer electrolyte layer.
Respectively pouring dispersion liquid containing 0.25 wt% of zinc trifluoromethanesulfonyl imide at two sides of the PVDF-NaTFSI polymer electrolyte layer, and forming a film on the surface of the PVDF-NaTFSI polymer electrolyte layer by 0.25 wt% of zinc dimethacrylate modified electrolyte when the N, N-dimethylformamide solvent is volatilized, wherein the film thickness at two sides is 8 micrometers respectively, so as to obtain the composite electrolyte layer 1. It was used as a solid electrolyte to assemble a sodium-sodium half cell, designated as metal sodium half cell III.
Compounding 0.25 wt% of zinc trifluoromethanesulfonylimide modified polymer electrolyte membrane on one side surface of the PVDF-NaTFSI polymer electrolyte layer according to the same method, wherein the membrane thickness is 8 microns to obtain a composite electrolyte layer 2, taking the composite electrolyte layer as a solid electrolyte, enabling the 0.25 wt% of zinc trifluoromethanesulfoniylimide modified polymer electrolyte membrane to be close to a metal sodium cathode, and adopting LiFePO as an anode4And (3) assembling an active material into a positive electrode/solid electrolyte/metallic sodium negative electrode all-solid-state battery, marking as a metallic sodium all-solid-state battery III, and testing the cycle performance of the metallic sodium all-solid-state battery III at 50 ℃.
The water content is controlled to be less than 1ppm in the whole process.
Comparative example 3
Referring to example 3, PVDF and NaTFSI electrolyte (PVDF and NaTFSI mass ratio is 640:296) which do not contain zinc trifluoromethanesulfonylimide are dissolved in N, N-dimethylformamide together, then the solution is placed in a polytetrafluoroethylene mold, and a film is formed independently after the N, N-dimethylformamide solvent is volatilized, and the thickness of the electrolyte is controlled to be 96-116 micrometers, so that a polymer electrolyte layer 1 is obtained. The composite electrolyte layer 1 of example 3 was replaced with the polymer electrolyte layer 1 and a sodium metal/solid electrolyte/sodium metal half cell, designated as sodium metal half cell III', was assembled as in example 3.
Referring to example 3, PVDF and NaTFSI electrolyte (PVDF to NaTFSI mass ratio of 640:296) without zinc trifluoromethanesulfonylimide were dissolved together in N, N-dimethylformamide, and then placed in a teflon mold, and a film was formed separately after the N, N-dimethylformamide solvent was volatilized, and the thickness of the electrolyte was controlled to 88 to 108 μm, to obtain a polymer electrolyte layer 2. The composite electrolyte layer 2 of example 3 was replaced with the polymer electrolyte layer 2, and a positive electrode/solid electrolyte/metallic sodium full cell, designated as metallic sodium full cell III', was assembled according to the method of example 3 and tested for 50 ℃ cycle performance.
Example 4
Dissolving 0.44g of PEO and 0.19g of KTFSI electrolyte in acetonitrile, stirring for more than 24h at 30 ℃, adding zinc stearate (the mass amount of the zinc stearate is 1 wt% of the total mass of the PEO and the KTFSI) while stirring for 10h, and uniformly mixing to obtain a dispersion liquid for modifying the PEO-KTFSI electrolyte.
Dissolving PEO and KTFSI (the mass ratio of PEO to KTFSI is 44:19) in an acetonitrile solvent together, then placing the mixture in a polytetrafluoroethylene mold, and controlling the thickness of the mixture to be 90-100 microns when the acetonitrile solvent is volatilized to form a film independently to obtain the PEO-KTFSI polymer electrolyte layer.
Respectively pouring dispersion liquid containing 1 wt% of zinc stearate on two sides of the PEO-KTFSI polymer electrolyte layer, and after an acetonitrile solvent is volatilized, enabling the electrolyte modified by the 1 wt% of zinc stearate to form a film on the surface of the PEO-KTFSI polymer electrolyte layer, wherein the film thickness of the two sides is 5 micrometers respectively, so as to obtain the composite electrolyte layer 1. It was used as a solid electrolyte to assemble a potassium-potassium half cell, designated as potassium metal half cell IV.
Compounding a polymer electrolyte membrane modified by zinc stearate on the single-side surface of the PEO-KTFSI polymer electrolyte layer according to the same method, wherein the thickness of the membrane layer is 5 microns to obtain a composite electrolyte layer 2, taking the composite electrolyte layer as a solid electrolyte, enabling the polymer electrolyte membrane modified by the zinc stearate to be close to a metal potassium cathode, and adopting LiFePO as an anode4And (3) assembling an active material, namely assembling a positive electrode/solid electrolyte/potassium metal negative electrode all-solid-state battery, recording as a potassium metal all-solid-state battery IV, and testing the cycle performance of the potassium metal all-solid-state battery at 50 ℃.
The water content is controlled to be less than 1ppm in the whole process.
Comparative example 4
Referring to example 4, PEO not containing zinc stearate and KTFSI electrolyte (the mass ratio of PEO to KTFSI is 44:19) are dissolved together in acetonitrile solvent, then placed in a polytetrafluoroethylene mold, and independently formed into a film after the acetonitrile solvent is volatilized, and the thickness of the electrolyte is controlled to be 100-110 microns, so that the polymer electrolyte layer 1 is obtained. The composite electrolyte layer 1 of example 4 was replaced with a polymer electrolyte layer 1, and a potassium metal/solid electrolyte/potassium metal half cell, denoted as potassium metal half cell IV', was assembled as in example 4.
Referring to example 4, PEO not containing zinc stearate and KTFSI electrolyte (the mass ratio of PEO to KTFSI is 44:19) were dissolved together in acetonitrile solvent, and then placed in a polytetrafluoroethylene mold, and a film was formed separately after the acetonitrile solvent was volatilized, and the thickness of the electrolyte was controlled to 95 to 105 μm, to obtain a polymer electrolyte layer 2. The composite electrolyte layer 2 of example 4 was replaced with the polymer electrolyte layer 2, and a positive electrode/solid electrolyte/potassium metal full cell, designated as potassium metal full cell IV', was assembled in accordance with the method of example 4 and tested for 50 c cycle performance.
Example 5
Dissolving 0.53g of PAN and 0.191g of LiTFSI together in 10ml of N, N-dimethylformamide solvent, stirring at 80 ℃ for more than 24h, adding propineb (the mass amount of which is 0.5 wt% of the total mass of the PAN and the LiTFSI) while stirring for 10h for modifying PAN-LiTFSI electrolyte, then placing the PAN-LiTFSI electrolyte in a polytetrafluoroethylene mold, and independently forming a film after the N, N-dimethylformamide solvent is volatilized to obtain a Zn salt modified polymer electrolyte film, wherein the thickness of the film is 10 microns.
By adopting a similar method, dissolving the PAN and LiTFSI electrolytes (the mass ratio of the PAN to the LiTFSI is 530:191) without containing propineb into an N, N-dimethylformamide solvent, then placing the solution into a polytetrafluoroethylene mold, independently forming a film after the N, N-dimethylformamide volatilizes, and controlling the thickness of the electrolyte to be 75-80 microns to obtain the PAN-LiTFSI polymer electrolyte layer.
And compounding a Zn salt modified polymer electrolyte membrane on the two side surfaces of the PAN-LiTFSI polymer electrolyte layer, standing for 1h at 60 ℃ to obtain a composite electrolyte layer 1, and taking the composite electrolyte layer as a solid electrolyte to assemble a metal lithium/solid electrolyte/metal lithium half-cell, which is marked as a metal lithium half-cell V.
In PAN-LiTFSI polymersCompounding a polymer electrolyte membrane modified by Zn salt on one side surface of the electrolyte layer, standing at 60 ℃ for 1h to obtain a composite electrolyte layer 2, taking the composite electrolyte layer as a solid electrolyte, enabling the polymer electrolyte membrane modified by Zn salt to be close to a metal lithium cathode, and adopting LiFePO as an anode4And (3) assembling an active material, namely assembling a positive electrode/solid electrolyte/lithium metal negative electrode all-solid-state battery, marking as a lithium metal all-solid battery V, and testing the cycle performance of the lithium metal all-solid-state battery at 50 ℃.
The water content is controlled to be less than 1ppm in the whole preparation process.
Comparative example 5
Referring to example 5, propineb-free PAN and LiTFSI (PAN and LiTFSI in a mass ratio of 530:191) were dissolved together in N, N-dimethylformamide solvent, and then placed in a polytetrafluoroethylene mold, and a film was formed separately after N, N-dimethylformamide was volatilized, and the thickness of the electrolyte was controlled to 95 to 100 μm, to obtain a polymer electrolyte layer 1. A lithium metal/solid electrolyte/lithium metal half cell, denoted as lithium metal half cell V', was assembled as in example 5, replacing the composite electrolyte layer 1 in example 5 with a polymer electrolyte layer 1.
Dissolving PAN and LiTFSI electrolyte (the mass ratio of PAN to LiTFSI is 530:191) which do not contain propineb into N, N-dimethylformamide solvent, then placing the mixture into a polytetrafluoroethylene mold, and independently forming a film after N, N-dimethylformamide volatilizes, wherein the thickness of the electrolyte is controlled to be 85-90 micrometers, so as to obtain the polymer electrolyte layer 2. The composite electrolyte layer 2 of example 5 was replaced with the polymer electrolyte layer 2, and a positive electrode/solid electrolyte/lithium metal negative electrode all-solid-state battery, designated as lithium metal all-solid battery V', was assembled according to the method of example 5 and tested for 50 ℃ cycle performance.
FIG. 5 shows the stability of PAN-LiTFSI electrolytes with and without propineb modification of example 5 and comparative example 5 to metallic lithium at 50 ℃ at a current density of 0.1mA cm-2Capacity of 0.1mAh cm-2The metal lithium half-cells V and V 'are tested under the condition, and as can be seen from the figure, the half-cell V' without the electrolyte assembly modified by Zn salt can only be stably circulated for 170h, and the cycle life of the lithium-lithium cell can be doubled by the modification of propineb, and the stable circulation is more than 350 h. It can be seen that Zn salt stabilized electrolyte and metallic lithiumPositive effect of the interface.
Claims (10)
1. A method of stabilizing a solid electrolyte/metal anode interface with a zinc salt, the method comprising the steps of:
(1) preparing a polymer electrolyte layer;
(2) adding Zn salt in the preparation process of the polymer electrolyte, and drying with a solvent to obtain the Zn salt modified polymer electrolyte, wherein the mass content of the Zn salt is controlled to be 0.1-3%;
(3) compounding the Zn salt modified polymer electrolyte prepared in the step (2) on the surface of the polymer electrolyte layer prepared in the step (1) to form a composite electrolyte layer, and assembling a solid-state metal battery by taking the composite electrolyte layer as a solid-state electrolyte, wherein the Zn salt modified polymer electrolyte is positioned between the polymer electrolyte layer and a metal electrode;
the Zn salt is selected from one or more of zinc trifluoromethanesulfonate, zinc perchlorate, propineb, zinc dimethacrylate, zinc trifluoromethanesulfonylimide and zinc stearate.
2. The method of claim 1, wherein: the polymer electrolyte layer has a thickness of 70 to 100 micrometers.
3. The method of claim 1 or 2, wherein: the thickness of a film layer formed by the Zn salt modified polymer electrolyte is less than 20 microns.
4. The method of claim 3, wherein: the thickness of a film layer formed by the Zn salt modified polymer electrolyte is 10-15 microns.
5. The method of any of claims 1-4, wherein: in the steps (1) and (2), the polymer electrolyte is a polymer electrolyte suitable for a solid metal battery, the solid metal battery is a solid metal lithium battery, a solid metal sodium battery or a solid metal potassium battery, and the polymer electrolyte comprises a polymer and a corresponding polymerThe conductive metal salt is conductive lithium salt or conductive sodium salt or conductive potassium salt, the mass ratio of the polymer to the conductive metal salt is 5:1-20:1, the polymer is one or the combination of more than two of polyethylene oxide (PEO), Polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF), and the conductive lithium salt is LiTFSI, LiFSI or LiClO4One or the combination of more than two of LiBOB and LiDFOB, and the conductive sodium salt is NaTFSI, NaFSI and NaClO4One or more of NaBOB and NaDFOB, wherein the conductive potassium salt is KTFSI, KFSI and KClO4One or a combination of more than two of KBOB and KDFOB.
6. The method of claim 5, wherein: the preparation method of the Zn salt modified polymer electrolyte comprises the following steps: and (2) dissolving the polymer, the conductive metal salt and the Zn salt into acetonitrile, N-dimethylformamide, N-methylpyrrolidone, acetone or methanol to obtain a mixed solution, placing the mixed solution into a polytetrafluoroethylene mold, and volatilizing the solvent to obtain the Zn salt modified polymer electrolyte.
7. The method of any of claims 1-4, wherein: in the step (2), the mass content of the Zn salt in the Zn salt modified polymer electrolyte is 0.5%.
8. The method of any of claims 1-4, wherein: in the step (3), the Zn salt modified polymer electrolyte prepared in the step (2) is compounded on the surface of the polymer electrolyte layer prepared in the step (1) to form a composite electrolyte layer in one of the following two ways:
independently forming a film by using a polymer electrolyte modified by Zn salt, then pasting the film on the surface of the polymer electrolyte layer prepared in the step (1), and standing for more than 1h at the temperature of 60-80 ℃;
preparing the Zn salt modified polymer electrolyte prepared in the step (2) into dispersion liquid, then pouring the dispersion liquid onto the surface of the polymer electrolyte layer prepared in the step (1), and volatilizing the solvent to form a film layer.
9. The method of any of claims 1-4, wherein: in the step (3), the positive electrode is LiNi1/3Co1/ 3Mn1/3O2NCM811, NCM523 or LiFePO4The metal negative electrode is metal lithium, metal sodium and metal potassium.
10. The method of any of claims 1-4, wherein: the environmental water content needs to be controlled to less than 1ppm during both the preparation of the polymer electrolyte and the assembly of the battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011577323.9A CN112687960A (en) | 2020-12-28 | 2020-12-28 | Method for stabilizing solid electrolyte/metal negative electrode interface by using zinc salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011577323.9A CN112687960A (en) | 2020-12-28 | 2020-12-28 | Method for stabilizing solid electrolyte/metal negative electrode interface by using zinc salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112687960A true CN112687960A (en) | 2021-04-20 |
Family
ID=75452366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011577323.9A Pending CN112687960A (en) | 2020-12-28 | 2020-12-28 | Method for stabilizing solid electrolyte/metal negative electrode interface by using zinc salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112687960A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060204846A1 (en) * | 2005-03-11 | 2006-09-14 | Takuya Sunagawa | Lithium secondary battery |
| CN106797021A (en) * | 2014-10-09 | 2017-05-31 | 宝马股份公司 | Additive based on alkali metal, the accumulator for being based especially on lithium |
| CN107636880A (en) * | 2015-10-30 | 2018-01-26 | 株式会社Lg化学 | Polymer dielectric with sandwich construction and include its all-solid-state battery |
| CN107732297A (en) * | 2017-10-13 | 2018-02-23 | 中国科学院青岛生物能源与过程研究所 | A kind of high voltage withstanding multilevel hierarchy composite solid electrolyte applied to lithium battery |
| CN108539272A (en) * | 2018-05-10 | 2018-09-14 | 清华大学 | A kind of electrolyte of lithium metal battery |
| CN109301317A (en) * | 2018-08-20 | 2019-02-01 | 浙江工业大学 | A kind of preparation method of high pressure resistant solid polymer electrolyte |
| CN109565078A (en) * | 2017-06-20 | 2019-04-02 | 株式会社Lg化学 | The copolymer solid electrolyte of multilayered structure and all-solid-state battery comprising it |
| CN111799466A (en) * | 2020-06-28 | 2020-10-20 | 浙江工业大学 | Flexible solid-state battery containing electron conduction interface layer and preparation method thereof |
-
2020
- 2020-12-28 CN CN202011577323.9A patent/CN112687960A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060204846A1 (en) * | 2005-03-11 | 2006-09-14 | Takuya Sunagawa | Lithium secondary battery |
| CN106797021A (en) * | 2014-10-09 | 2017-05-31 | 宝马股份公司 | Additive based on alkali metal, the accumulator for being based especially on lithium |
| CN107636880A (en) * | 2015-10-30 | 2018-01-26 | 株式会社Lg化学 | Polymer dielectric with sandwich construction and include its all-solid-state battery |
| CN109565078A (en) * | 2017-06-20 | 2019-04-02 | 株式会社Lg化学 | The copolymer solid electrolyte of multilayered structure and all-solid-state battery comprising it |
| CN107732297A (en) * | 2017-10-13 | 2018-02-23 | 中国科学院青岛生物能源与过程研究所 | A kind of high voltage withstanding multilevel hierarchy composite solid electrolyte applied to lithium battery |
| CN108539272A (en) * | 2018-05-10 | 2018-09-14 | 清华大学 | A kind of electrolyte of lithium metal battery |
| CN109301317A (en) * | 2018-08-20 | 2019-02-01 | 浙江工业大学 | A kind of preparation method of high pressure resistant solid polymer electrolyte |
| CN111799466A (en) * | 2020-06-28 | 2020-10-20 | 浙江工业大学 | Flexible solid-state battery containing electron conduction interface layer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| GEORGE V. ALEXANDER，ETC: "Interface-Compatible and High-Cyclability Lithiophilic Lithium−Zinc", 《ACS APPLIED ENERGY MATERIALS》 * |
| TIEFENG LIU，ETC: "In-situ construction of a Mg-modified interface to guide uniform lithium deposition for stable all-solid-state batteries", 《JOURNAL OF ENERGY CHEMISTRY》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11283078B2 (en) | Aqueous slurry for battery electrodes | |
| US6280882B1 (en) | Electrolytic composition with polymer base for electrochemical generator | |
| CN109065945A (en) | A kind of solid electrolyte membrane and its preparation method and application | |
| KR100291067B1 (en) | Pre-lithiation method of carbon electrodes and its application to assembling lithium secondary batteries | |
| CN111244537A (en) | Composite solid electrolyte, solid battery and preparation method thereof | |
| EP3469648A1 (en) | High energy density, high power density, high capacity, and room temperature capable "anode-free" rechargeable batteries | |
| US20150311492A1 (en) | High Energy Density Charge And Discharge Lithium Battery | |
| CN112018430A (en) | Composite solid electrolyte prepared based on in-situ thermal polymerization method and preparation method and application thereof | |
| CN107078343A (en) | Lithium-sulfur cell | |
| CN109904514A (en) | Two-layer compound solid electrolyte and its preparation method and application | |
| CN105164832A (en) | Positive electrode for a lithium battery | |
| CN111799503A (en) | NASICON type electrolyte-based composite solid electrolyte film and preparation method thereof | |
| US20210083317A1 (en) | Lithium ion conductive composite material for all solid-state lithium battery, and solid polymer electrolyte and all solid-state lithium battery including the same | |
| CN111725559A (en) | Solid electrolyte, method for preparing the same, and lithium secondary solid battery | |
| CN108428935A (en) | A kind of solid electrolyte membrane preparation method and lithium battery | |
| CN112467193A (en) | Safety lithium ion battery and preparation method thereof | |
| CN114335700A (en) | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method | |
| KR20170050278A (en) | Polymer Electrolyte comprising Lithium Nitrate and All-Solid-State Battery comprising The Same | |
| KR20160051609A (en) | Lithium secondary battery and method for manufacturing the same | |
| US20220271280A1 (en) | A lithium negative electrode with protective layer, preparation method and application thereof | |
| CN112768753A (en) | Preparation method of solid electrolyte and solid battery | |
| CN112687960A (en) | Method for stabilizing solid electrolyte/metal negative electrode interface by using zinc salt | |
| CN115832412A (en) | Composite solid electrolyte and preparation method and application thereof | |
| CN114447405A (en) | Inorganic ceramic ion conductor based composite solid electrolyte film and preparation method thereof | |
| CN113764822A (en) | High-ionic-conductivity composite coating film for lithium primary battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210420 |
|
| RJ01 | Rejection of invention patent application after publication |