CN114284547A - Polyvalent metal battery containing two-dimensional nanosheet additive - Google Patents
Polyvalent metal battery containing two-dimensional nanosheet additive Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 239000002135 nanosheet Substances 0.000 title claims abstract description 52
- 239000000654 additive Substances 0.000 title claims abstract description 36
- 230000000996 additive effect Effects 0.000 title claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 62
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910052582 BN Inorganic materials 0.000 claims abstract description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 29
- 229910052725 zinc Inorganic materials 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002055 nanoplate Substances 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 abstract description 22
- 238000000151 deposition Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910018628 Al(CF3SO3)3 Inorganic materials 0.000 description 1
- 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 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019389 Mg(CF3SO3)2 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a polyvalent metal battery containing a two-dimensional nanosheet additive, which comprises an electrolyte and a polyvalent metal cathode, wherein the electrolyte comprises electrolyte salt, the two-dimensional nanosheet additive and a solvent; the two-dimensional nanosheet additive is selected from one or more of carbon nitride, boron nitride, nitrogen-doped graphene, sulfur-doped graphene and oxygen-doped graphene. According to the invention, the two-dimensional nanosheet additive is added into the electrolyte, so that metal deposition can be sequentially induced on an electrochemical interface continuously to form a compact and ordered metal deposit, and thus the electrochemical performance and cycle life of a full battery based on polyvalent metal as a cathode are improved.
Description
Technical Field
The invention relates to the technical field of secondary high-energy density batteries, in particular to a polyvalent metal battery containing a two-dimensional nanosheet additive.
Background
With the rapid development of new energy science and technology industries such as portable electronic equipment, electric automobiles and the like, the world has high energyThere is an increasing demand for high-volume density, high-safety factor energy storage devices. Lithium batteries have a high energy density (200-300 Whkg)-1) And good cycle life (1000-1500 cycles) have become one of the most important energy storage devices at present, but are limited by the rare earth crust lithium source storage capacity (0.0065 wt%) and the highly combustible characteristics of electrode materials and organic electrolyte, and the large-scale deep popularization and application of lithium batteries are limited. Zinc metal (Zn/Zn) based on multiple electron transfer2+) Magnesium metal (Mg/Mg)2 +) And aluminum metal (Al/Al)3+) The cathode is characterized in that: (1) abundant crustal resource reserves; (2) extremely high specific capacity of quality; (3) the air stability is good, and the combustion and explosion hidden danger is avoided, so that the air-conditioning system is hopeful to become the selection of the next generation of energy storage equipment.
However, almost all metallic negative electrodes (lithium, sodium, potassium, magnesium, zinc, copper, aluminum, etc.) tend to form loose and uneven metallic deposits during electrodeposition, and may even form acicular deposits. The disordered and loose deposition mode can easily cause that the metal cathode is difficult to maintain an ordered electronic path in the dynamic circulation process, thereby causing short circuit of the battery, poor electrochemical reversibility of the metal cathode or extremely low efficiency of active substances, and the like. The ordered deposition of alkali metal can be effectively promoted by constructing the functional conductive coating on the surface of the current collector. Such as: the graphene coating can effectively promote ordered epitaxial growth of metal zinc on the surface of the metal zinc, so as to promote dense deposition of new metal (Reversible epitaxial electrochemical deposition of metals in batteries, science2019, 366,645); gold nanoplatelets coatings can promote ordered deposition on metallic aluminum surfaces (modulating the growth of aluminum electrodes: surfaces anode-free Al batteries J. Mater. chem. A., 2020,8, 23231). This functional coating fixed to the current collector is covered by the deposited metal as the electrodeposition process proceeds, gradually losing control over the metal deposition. The continuous orderly control of metal deposition in the deposition process has great significance for the construction of deep-cycle secondary high-energy density alkali metal batteries.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a polyvalent metal battery containing a two-dimensional nanosheet additive.
The specific technical scheme is as follows:
a polyvalent metal battery containing a two-dimensional nanosheet additive comprises an electrolyte and a polyvalent metal cathode, wherein the electrolyte comprises an electrolyte salt, the two-dimensional nanosheet additive and a solvent;
the two-dimensional nanosheet additive is selected from one or more of carbon nitride, boron nitride, nitrogen-doped graphene, sulfur-doped graphene and oxygen-doped graphene.
The polyvalent metal negative electrode is selected from one or more of a zinc metal negative electrode, a magnesium metal negative electrode and an aluminum metal negative electrode.
The invention discloses a polyvalent metal battery which is formed by assembling a metal cathode, an anode and electrolyte, wherein a specific two-dimensional nanosheet additive is added into the electrolyte. The polyvalent metal zinc, magnesium, aluminum and other metal cathodes have higher electrochemical potential and weak chemical reactivity, so that an interface passivation layer cannot be generated, in the dynamic charging and discharging process of the battery, the specific two-dimensional nanosheet additive selected by the invention can specifically adsorb the crystal face with the lowest surface energy of deposited metal (such as hexagonal zinc metal, magnesium metal and the crystal face with the lowest surface energy of 0002 crystal face), then the metal is guided to be orderly and dynamically deposited along the two-dimensional nanosheets, and in the discharging metal stripping process, the two-dimensional nanosheets are stripped and dissolved out along with the metal and are re-dispersed in the electrolyte.
The electrolyte salt is selected from one or more of zinc salt, magnesium salt and aluminum salt. The kind of the electrolyte salt in the present invention is not particularly limited, and may be selected from those commonly used in the art. For example, the zinc salt may be selected from ZnCl2、Zn(CF3SO3)2、Zn(CF3SO2N)2、ZnSO4、Zn(CH3COO)2Etc.; the magnesium salt can be selected from MgCl2、Mg(CF3SO3)2、Mg(CF3SO2N)2、MgSO4、Mg(BH4)2、Mg(CH3COO)2Etc.; the aluminum salt can be selected from AlCl3、Al(CF3SO3)3、Al(CF3SO2N)3、Al2(SO4)3、Al(BH4)3、Al(CH3COO)3And the like.
The solvent may be selected from water, and may also be selected from one or more of organic solvents, such as 1,3 dioxolane, ethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, methyl ethyl carbonate, dimethyl sulfoxide, sulfolane, dimethylformamide, acetone, ethanol, methanol, hexafluoroisopropanol, triethyl phosphate, urea, ethylurea, 1-ethyl-3-methylimidazolium chloride.
The preparation of the electrolyte comprises the following steps:
mixing a two-dimensional nanosheet additive, an electrolyte salt and a solvent, and ultrasonically dispersing for 1-6 hours at the temperature of 0-60 ℃.
Preferably:
in the electrolyte, the molar concentration of electrolyte salt is 0.1-20.0 mol L-1(ii) a More preferably 0.5 to 10.0mol L-1。
In the electrolyte, the concentration of the two-dimensional nanosheet additive is 0.1-50 mg/mL; tests show that the multivalent metal cathode has higher coulombic efficiency, namely higher utilization rate of active substances, along with the increase of the concentration of the two-dimensional nanosheet additive in the electrolyte; however, the mutual coulomb effect among the two-dimensional nano sheets can be caused by too high concentration, so that the two-dimensional nano sheet additive is settled in the electrolyte; more preferably 0.1 to 1.0 mg/mL.
Preferably, the two-dimensional nanosheet additive has a large width/thickness ratio, with a width of 5nm to 50 μm and a thickness of 0.1 to 50 nm.
Still more preferably:
the two-dimensional nanoplate additive is selected from carbon nitride;
the polyvalent metal negative electrode is selected from a zinc metal negative electrode;
the concentration of the two-dimensional nanosheet additive is 0.5-1.0 mg/mL.
More preferably, the concentration of the two-dimensional nanoplatelet additive is 1.0 mg/mL.
Tests show that the assembled polyvalent metal battery has excellent electrochemical performance and cycle life by adopting the further optimized raw material types and the further optimized amount.
The polyvalent metal battery disclosed by the invention also comprises a positive electrode and a diaphragm, wherein the positive electrode is selected from ZnxV2O5nH2O、MnO2Sulfur, graphene and the like, and the diaphragm is selected from common types such as a glass fiber film, a polypropylene film and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention discloses a polyvalent metal battery containing a two-dimensional nanosheet additive, wherein the two-dimensional nanosheet additive is added into an electrolyte, and the electrolyte is adsorbed on a metal specific crystal face through a specific adsorption effect in an electrodeposition process, so that metal deposition is dynamically regulated, compact and ordered metal deposition is promoted, generation of loose and uneven metal deposition is inhibited, and the safety of the battery is improved. The active substance of the compact and ordered metal deposition has high utilization rate in the discharging process, and can slow down the electrochemical inactivation of the active substance, thereby improving the electrochemical performance and cycle life of the whole polyvalent metal battery;
2. the multivalent metal battery disclosed by the invention is compatible with the current lithium ion battery process technology and has commercial potential.
3. The polyvalent metal battery disclosed by the invention has excellent cathode coulombic efficiency which can reach more than 99%, and excellent cycling stability.
Drawings
Fig. 1 is a scanning electron microscope zinc metal deposition diagram of a first circle of deposition in an electrolyte containing two-dimensional nanosheets of example 1, and a is zinc metal deposition at a cross-sectional view angle; b is the zinc metal deposition of the overlooking visual angle;
fig. 2 is a picture of an atomic force-infrared combined spectrum of the first circle deposition in the electrolyte containing the two-dimensional nanosheets of example 1, wherein in the a picture, 1, 2 and 3 are infrared absorption spectra of a zinc metal deposition side edge, a top end and a side edge respectively; b, zinc metal deposition at different positions;
FIG. 3 is a surface topography of zinc metal deposition after a first cycle of deposition in the electrolyte containing two-dimensional nanosheets of example 1 (a diagram); and vibration (1637 cm) corresponding to the carbon-nitrogen bond characteristic of the carbon nitride two-dimensional nanosheet in the a diagram-1) Infrared spectral surface scan (panel b);
FIG. 4 is a scanning electron microscope lithium metal deposition map of a first cycle deposition in a reference electrolyte without two-dimensional nanoplatelets of comparative example 1, a being cross-sectional view zinc metal deposition; b is the zinc metal deposition of the overlooking visual angle;
fig. 5 is a cycle performance graph of a full cell assembled with the two-dimensional nanosheet electrolyte of example 2, and is given as a comparison (denoted as reference) the cycle performance graph of a full cell assembled with comparative example 2;
FIG. 6 is a graph showing cycle performance of the full cells respectively assembled in examples 7 to 10, and is given as a comparison with comparative example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The formulation contains 2.0mol L-1ZnSO4，0.5mg mL-1And (3) ultrasonically dispersing the carbon nitride two-dimensional nanosheet electrolyte and water as a solvent at 25 ℃ for 1 hour until the dispersion is uniform to form a colloidal electrolyte.
The electrolyte is used for taking a zinc metal foil with the thickness of 100 mu m as a battery cathode, and the using surface capacity of the anode is 1mAh cm-2MnO of2As the positive electrode, the glass fiber membrane is used as the diaphragm, and the battery tester is provided withWuhan blue electricity company) constant current 1.0C, the coulomb efficiency of the battery can reach 99.9%, and the cycle life is 1500 circles.
Fig. 1 is a scanning electron microscope zinc metal deposition diagram of the first circle of deposition in the electrolyte of this embodiment, and it can be found through observation that, by using the electrolyte added with carbon nitride two-dimensional nanosheets in the present invention, zinc metal is deposited compactly and in an ordered arrangement.
Fig. 2 is an atomic force-infrared combined spectrum picture of the first circle of deposition in the electrolyte of the embodiment, and observation shows that carbon nitride two-dimensional nanosheet infrared signals exist on both sides of zinc metal deposition, which indicates that the carbon nitride nanosheets can be selectively adsorbed on a specific crystal face of zinc metal and co-deposited in the metal deposition.
FIG. 3 is a surface topography of zinc metal deposition after the first deposition in the electrolyte and the vibration of carbon-nitrogen bond characteristic of the carbon nitride two-dimensional nanosheet in the corresponding figure (1637 cm)-1) The ordered intercalation of the carbon nitride two-dimensional nano-sheets in the sediment can be observed by scanning the infrared spectrum surface.
Comparative example 1
The preparation process is basically the same as that of example 1, except that carbon nitride two-dimensional nanosheets are not added into the electrolyte. The full cell assembled in this comparative example, using the same test conditions as in example 1, had a coulombic efficiency of 99.1% and a cycle life of 560 cycles.
Fig. 4 is a scanning electron microscope image of lithium metal deposition from the first cycle of deposition in the reference electrolyte of this comparative example, and observation of this image reveals that zinc metal deposition is loose and disordered.
Example 2
The formulation contains 2.0mol L-1ZnSO4，1.0mg mL-1And (3) ultrasonically dispersing the carbon nitride two-dimensional nanosheet electrolyte and water as a solvent at 0 ℃ for 2 hours until the dispersion is uniform to form a colloidal electrolyte.
The electrolyte is used for taking a zinc metal foil with the thickness of 20 mu m as a battery cathode, and the using surface capacity of the anode is 6mAh cm-2Zn of (2)xV2O5 nH2O is the positive electrode, the glass fiber membrane is the diaphragm, and the constant current of 1.0C is charged and discharged on a battery tester (Wuhan blue-electricity company)The coulombic efficiency of the pool can reach 99.9%, and the cycle life is 400 circles.
Comparative example 2
The preparation process is basically the same as that of example 2, except that carbon nitride two-dimensional nanosheets are not added into the electrolyte. The full cell assembled in this comparative example, using the same test conditions as in example 2, had a coulombic efficiency of 99.5% and a cycle life of 36 cycles, and internal short circuits occurred in the cell.
Example 3
The preparation process is basically the same as that of the embodiment 2, and the difference is that the boron nitride two-dimensional nanosheet is added into the electrolyte.
The assembly and testing of the cell were exactly the same as in example 2, and the coulombic efficiency was 99.5% and the cycle life was 225 cycles, and an internal short circuit occurred in the cell.
Example 4
The formulation contains 6.0mol L-1ZnCl2，1.0mg mL-1And (3) ultrasonically dispersing the electrolyte of the carbon nitride two-dimensional nanosheet at 0 ℃ for 2 hours by using water/methanol (volume ratio of 1: 1) as a solvent until the dispersion is uniform to form a colloidal electrolyte.
The electrolyte is used for using a zinc metal foil with the thickness of 200 mu m as a battery cathode, and the using surface capacity of the anode is 1mAh cm-2MnO of2The anode is a single-layer polypropylene film, the battery is charged and discharged at constant current of 1.0C on a battery tester (Wuhan blue electric company), the coulombic efficiency of the battery can reach 99.9 percent, and the cycle life of the battery is 2430 circles.
Example 5
In an argon glove box, a solution containing 0.5mol of L-1MgCl2，0.5mol L-1Mg(CF3SO2N)2，1.0mg mL-1And (3) ultrasonically dispersing the electrolyte of the carbon nitride two-dimensional nanosheet and tetrahydrofuran as a solvent at 0 ℃ for 2 hours until the dispersion is uniform to form a colloidal electrolyte.
The electrolyte is used for taking a magnesium metal foil with the thickness of 200 mu m as a battery cathode, and the using surface capacity of the cathode is 1mAh cm-2The sulfur as positive electrode, the glass fiber membrane as diaphragm, constant current 0.1C charging and discharging on a battery tester (Wuhan blue electric company)The coulombic efficiency of the pool can reach 99.9%, and the cycle life is 180 circles.
Example 6
Preparing AlCl with a molar ratio in an argon glove box31-Ethyl-3-methylimidazolium chloride 1.5, 1.0mg mL-1And ultrasonically dispersing the electrolyte of the carbon nitride two-dimensional nano sheet for 2 hours at the temperature of 0 ℃ until the dispersion is uniform, so as to form a colloidal electrolyte.
The electrolyte is used for taking 500 mu m thick aluminum foil as a battery cathode, and the using surface capacity of the cathode is 1mAh cm-2The graphene is used as a positive electrode, the glass fiber membrane is used as a diaphragm, constant current 2.0C charging and discharging are carried out on a battery tester (Wuhan blue electric company), the coulomb efficiency of the battery can reach 99.9%, and the cycle life is 3600 circles.
Example 7
The formulation contains 2.0mol L-1ZnSO4，1.0mg mL-1And (3) ultrasonically dispersing the carbon nitride two-dimensional nanosheet electrolyte and water as a solvent at 0 ℃ for 2 hours until the dispersion is uniform to form a colloidal electrolyte.
The electrolyte is used for taking a zinc metal foil with the thickness of 200 mu m as a battery cathode, a copper metal foil as an anode, a glass fiber film as a diaphragm and constant current of 4mA cm on a battery tester (Wuhan blue electric company)-2Charging and discharging with surface capacity of 1mAhcm-2。
Examples 8 to 10
The preparation process is basically the same as that of example 7, except that the concentration of the carbon nitride two-dimensional nanosheets in the electrolyte is respectively replaced by 0.1mg mL-1、0.3mg mL-1And 0.5mg mL-1。
The test conditions were exactly the same as in example 7.
Comparative example 3
The preparation process is basically the same as that of example 7, except that carbon nitride two-dimensional nanosheets are not added into the electrolyte. The cycle life curve of the full cell assembled in this comparative example, using the same test conditions as in example 7, is shown as the reference in fig. 6.
FIG. 6 is a graph showing cycle performance of the full cells assembled in examples 7 to 10 and comparative example 3,
tests show that the zinc metal cathode has higher coulombic efficiency along with the increase of the concentration of the two-dimensional nanosheets in the electrolyte, namely the utilization rate of active substances is higher; while example 7 used 1.0mg mL-1The electrolyte of the carbon nitride two-dimensional nanosheet exhibits an optimal cycle life of 1600 cycles.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A polyvalent metal battery containing a two-dimensional nanosheet additive comprises an electrolyte and a polyvalent metal cathode, and is characterized in that the electrolyte comprises electrolyte salt, the two-dimensional nanosheet additive and a solvent;
the two-dimensional nanosheet additive is selected from one or more of carbon nitride, boron nitride, nitrogen-doped graphene, sulfur-doped graphene and oxygen-doped graphene.
2. The multivalent metal cell of claim 1 wherein the electrolyte salt is selected from one or more of a zinc salt, a magnesium salt, and an aluminum salt.
3. The multivalent metal cell with two-dimensional nanoplate additive of claim 1 wherein the solvent is selected from one or more of water, 1,3 dioxolane, ethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, methyl ethyl carbonate, dimethyl sulfoxide, sulfolane, dimethylformamide, acetone, ethanol, methanol, hexafluoroisopropanol, triethyl phosphate, urea, ethylurea, 1-ethyl-3-methylimidazolium chloride.
4. According to claim 1The polyvalent metal battery containing the two-dimensional nanosheet additive is characterized in that the molar concentration of electrolyte salt in the electrolyte is 0.1-20.0 mol L-1The concentration of the two-dimensional nanosheet additive is 0.1-50 mg/mL.
5. The multivalent metal battery comprising a two-dimensional nanoplate additive of claim 1 wherein the multivalent metal anode is selected from one or more of a zinc metal anode, a magnesium metal anode, an aluminum metal anode.
6. A multivalent metal battery comprising a two dimensional nanoplate additive as claimed in any of claims 1 to 5 wherein the concentration of the two dimensional nanoplate additive is 0.1 to 1.0 mg/mL.
7. The multivalent metal cell of claim 6 comprising a two-dimensional nanoplate additive, wherein:
the two-dimensional nanoplate additive is selected from carbon nitride;
the polyvalent metal negative electrode is selected from zinc metal negative electrodes.
8. The multivalent metal cell of claim 7 comprising a two-dimensional nanoplate additive, wherein the concentration of the two-dimensional nanoplate additive is 0.5-1.0 mg/mL.
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| CN112919534A (en) * | 2021-01-29 | 2021-06-08 | 山东大学 | Zinc ion battery electrolyte modifier and preparation method and application thereof |
| CN113241475A (en) * | 2021-05-07 | 2021-08-10 | 中国科学院电工研究所 | Solid electrolyte and preparation method and application thereof |
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| CN112919534A (en) * | 2021-01-29 | 2021-06-08 | 山东大学 | Zinc ion battery electrolyte modifier and preparation method and application thereof |
| CN113241475A (en) * | 2021-05-07 | 2021-08-10 | 中国科学院电工研究所 | Solid electrolyte and preparation method and application thereof |
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