CN114865108B - Alkali metal battery electrolyte additive, electrolyte, and preparation and application thereof - Google Patents
Alkali metal battery electrolyte additive, electrolyte, and preparation and application thereof Download PDFInfo
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- CN114865108B CN114865108B CN202210522992.9A CN202210522992A CN114865108B CN 114865108 B CN114865108 B CN 114865108B CN 202210522992 A CN202210522992 A CN 202210522992A CN 114865108 B CN114865108 B CN 114865108B
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- alkali metal
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- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 123
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 105
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 80
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 Lewis base anions Chemical class 0.000 claims abstract description 60
- 239000003960 organic solvent Substances 0.000 claims abstract description 41
- 239000012046 mixed solvent Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- 239000002879 Lewis base Substances 0.000 claims abstract description 6
- 239000002608 ionic liquid Substances 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- 229910052786 argon Inorganic materials 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052743 krypton Inorganic materials 0.000 claims description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052704 radon Inorganic materials 0.000 claims description 4
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 23
- 230000000996 additive effect Effects 0.000 abstract description 23
- 210000001787 dendrite Anatomy 0.000 abstract description 23
- 150000001768 cations Chemical class 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 49
- 239000010949 copper Substances 0.000 description 46
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- INRYEEIIXAOXBN-UHFFFAOYSA-N acetonitrile;copper(1+) Chemical compound [Cu+].CC#N INRYEEIIXAOXBN-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000007614 solvation Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 5
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 4
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- NOBZSXGFNYRDMS-UHFFFAOYSA-M acetonitrile;copper(1+);trifluoromethanesulfonate Chemical compound [Cu+].CC#N.CC#N.CC#N.CC#N.[O-]S(=O)(=O)C(F)(F)F NOBZSXGFNYRDMS-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000017066 negative regulation of growth Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/28—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/26—Selection of materials as electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to an electrolyte additive for an alkali metal battery, an electrolyte and preparation and application thereof, and belongs to the technical field of alkali metal batteries. The additive is an ionic liquid composed of tetra-acetonitrile copper (I) cations and fluorine-containing Lewis base anions, wherein the fluorine-containing Lewis base anions are more than one of tetrafluoroborate ions, hexafluorophosphate ions, trifluoromethane sulfonate ions, bistrifluoromethyl sulfonyl imide ions and difluoro sulfonyl imide ions. The electrolyte includes 0.5mg mL ‑1～2mg mL‑1 of the additive. And adding the additive into a mixed solvent consisting of alkali metal salt and organic solvent, uniformly mixing, and standing to obtain the electrolyte. The additive inhibits the growth of alkali metal dendrites and improves the electrochemical performance of the battery through the combined action of electrostatic shielding and stable SEI film formation.
Description
Technical Field
The invention relates to an electrolyte additive for an alkali metal battery, an electrolyte and preparation and application thereof, and belongs to the technical field of alkali metal batteries.
Background
An alkali metal battery generally refers to a battery in which the negative electrode of the battery is metallic lithium, sodium, potassium, and alloys thereof. The alkali metal has extremely high theoretical specific capacity, lower oxidation-reduction potential and lower density, so that the alkali metal battery taking the alkali metal as the negative electrode is considered as one of the most potential high specific energy storage devices, and has wide application prospect.
However, the alkali metal cell is difficult to be applied on a large scale due to its poor safety and unstable cycle performance. An important reason for affecting the performance of alkali metal batteries is their poor interfacial stability. In the first cycle charge and discharge process of an alkali metal battery, an electrode material and electrolyte react on a solid-liquid phase interface to form a passivation layer covered on the surface of the electrode material, wherein the passivation layer is called a solid electrolyte phase interface film (SEI film for short), and the main components of the passivation layer are small molecular organic matters, organic polymers and inorganic compounds containing alkali metals. The SEI film can isolate the alkali metal electrode in the inner layer of the film from the electrolyte, so that the continuous corrosion of the electrolyte is prevented, and the effect of protecting the alkali metal electrode is achieved. But the SEI film also reduces the ion transport energy barrier between the electrode and the electrolyte, consuming the electrolyte, affecting the performance of the battery. Therefore, a suitable SEI film should have the following properties (i) thin thickness, small electrolyte consumption, (ii) good stability, no continuous decomposition, good mechanical properties, chemical stability and electrochemical stability, (iii) high alkali metal ion conductivity, and (iv) compact structure.
However, the SEI film formed spontaneously by the alkali metal electrode and the electrolyte is unsatisfactory in terms of strength, toughness and the like. In the deposition/stripping process of alkali metal, uneven deposition of alkali metal causes growth of alkali metal dendrite, which easily causes cracking of the SEI film, thereby losing its protective effect. The main problems of dendrite growth are also that the active alkali metal is reduced due to dendrite growth, the energy density of the battery is reduced, and the battery is short-circuited due to the penetration of the separator by dendrite, so that fire explosion is caused, and the safety of the battery is reduced.
At present, research on inhibition of growth of alkali metal dendrites is mostly focused on adding a film forming additive to an electrolyte to improve components of an SEI film, improve properties of the SEI film in terms of mechanical strength and the like, and further prevent dendrites from further growing and from penetrating a separator. However, in the film forming additive used at present, the effective substances introduced into the additive for improving the film forming performance or the constructed nano structure interface layer has vulnerability, once the consumption of the effective substances introduced into the additive is finished or the nano structure interface layer is broken, the effect of inhibiting the growth of alkali metal dendrites is lost, and the growth of the alkali metal dendrites is further more severe, so that the electrochemical performance is reduced, and serious potential safety hazards are brought.
Disclosure of Invention
In view of the above, in order to solve the problem of growth of alkali dendrites in the alkali metal battery in the prior art, the present invention aims to provide an electrolyte additive for an alkali metal battery, an electrolyte, and preparation and application thereof, wherein the electrolyte additive is applied to the electrolyte of the alkali metal battery, and can inhibit growth of alkali dendrites, improve cycle life of the alkali metal battery, and improve electrochemical performance of the battery through the combined action of electrostatic shielding and stable SEI film formation. The SEI film and the alkali metal electrode can inhibit the growth of alkali metal dendrites, improve the safety of the battery and enable the battery to have good electrochemical performance.
In order to achieve the purpose of the invention, the following technical scheme is provided.
An alkali metal battery electrolyte additive is an ionic liquid composed of a copper (I) tetraacetonitrile cation (TAC cation) and a fluorine-containing Lewis base anion, wherein the fluorine-containing Lewis base anion is one or more of tetrafluoroborate ion (BF 4 -), hexafluorophosphate ion (PF 6 -), trifluoromethane sulfonate ion (CF 3SO3 -), bistrifluoromethyl sulfonyl imide ion (TFSI-) and difluoro sulfonyl imide ion (FSI-).
Preferably, the electrolyte additive is more than one of copper (I) tetrafluoroborate ([ (CH 3CN)4Cu]BF4), copper (I) hexafluorophosphate ([ (CH 3CN)4Cu]PF6) and copper (I) tetraacetonitrile trifluoromethane sulfonate ([ (CH 3CN)4Cu]CF3SO3)).
An alkali metal battery electrolyte comprises an organic solvent, an alkali metal salt and the electrolyte additive, wherein the concentration of the electrolyte additive in the electrolyte is 0.5mg mL -1～2mg mL-1.
The organic solvent and alkali metal salt are those used in alkali metal batteries in the prior art.
Preferably, the organic solvent is one or more of Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1, 3-Dioxolane (DOL), 4-methyl-1, 3-dioxolane (4-MeDOL), dimethoxymethane (DMM), ethylene glycol dimethyl ether (DME), 1, 2-Dimethoxypropane (DMP), diglyme (DG), N-methylpyrrolidone (NMP), propylene Carbonate (PC), ethylene Carbonate (EC), butylene Carbonate (BC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), dimethylformamide (DMF), γ -Butyrolactone (BL), methyl Acetate (MA) and Ethyl Acetate (EA).
Preferably, the alkali metal salt is one or more of alkali metal hexafluorophosphate, alkali metal tetrafluoroborate, alkali metal bistrifluoromethylsulfonylimine salt and alkali metal perchlorate.
More preferably, the organic solvent consists of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, or consists of 4-methyl-1, 3-dioxolane (4-MeDOL) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, or consists of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1:1, or consists of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, or consists of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) in a volume ratio of 1:1:1, the alkali metal salt is one of alkali metal hexafluorophosphate, alkali metal tetrafluoroborate, alkali metal bistrifluoromethylsulfide and alkali metal perchlorate, and the alkali metal salt is an alkali metal salt, and the concentration of alkali metal salt is 1/L in the electrolyte.
Preferably, the concentration of the electrolyte additive in the electrolyte is 1mg mL -1.
The preparation method of the electrolyte comprises the following steps:
(1) Adding alkali metal salt into an organic solvent in an inert gas atmosphere with oxygen and water content of less than 1ppm, and uniformly mixing to obtain a mixed solvent;
(2) Continuously adding the electrolyte additive into the mixed solvent in the inert gas atmosphere, uniformly mixing, and standing for 15-60 min to obtain the electrolyte;
The inert gas is helium, neon, argon, krypton, xenon or radon.
Preferably, in the step (2), the electrolyte additive and the mixed solvent are uniformly mixed by adopting a magnetic stirring and ultrasonic dispersing mode.
More preferably, in the step (2), magnetic stirring is performed for 1 hour, and then ultrasonic dispersion is performed for 1 hour, so that the electrolyte additive and the mixed solvent are uniformly mixed.
Before electrochemical circulation, in an inert gas atmosphere with oxygen and water content less than 1ppm, immersing an alkali metal electrode body in the electrolyte to pre-react the alkali metal and the electrolyte, wherein the reaction temperature is 20-65 ℃ and the reaction time is 0.5-2 h, and after the reaction is finished, an SEI film is formed on the surface of the alkali metal electrode body in situ, so that the alkali metal electrode with the SEI film is obtained;
The inert gas is helium, neon, argon, krypton, xenon or radon.
Preferably, the reaction time is 0.5h to 1h.
An alkali metal battery, the electrolyte of which is the electrolyte of the invention;
or the negative electrode in the battery is an alkali metal electrode with an SEI film;
or the electrolyte of the battery is the electrolyte of the invention and the negative electrode in the battery is the alkali metal electrode with the SEI film.
Advantageous effects
(1) The invention provides an alkali metal battery electrolyte additive, wherein anions of the additive are compatible with an alkali metal battery electrolyte system and are beneficial to providing additional fluorine elements for an SEI film forming process, cations of the additive are TAC cations, cuprous ions (Cu +) can be provided in a chemical reaction, and the fluorine elements in the electrolyte are promoted to generate alkali metal fluoride due to the adjustment of an electrolyte solvation structure by Cu +, so that the alkali metal fluoride is used as a component of the SEI film. The increase of the content of alkali metal fluoride in the SEI film increases the mechanical strength of the SEI film, can effectively inhibit the growth of alkali metal dendrites, and is beneficial to improving the conduction rate of alkali metal ions, thereby improving the cycle performance and the service life of the battery. Meanwhile, TAC cations can cover the tips of dendrites aggregated by negative charges through electrostatic adsorption to form an effective shielding effect, so that the continuous growth of dendrites is prevented, and the risk of cracking of the generated SEI film along with long-time circulation of an alkali metal battery is reduced. In summary, the electrolyte additive of the present invention is applied to the electrolyte of an alkali metal battery, and can improve the cycle life and the working performance of the alkali metal battery through the combined action of the electrostatic shielding and the formation of the stable SEI film.
(2) The invention provides an electrolyte, which is applied to an alkali metal battery due to the electrolyte additive, so that the growth of alkali metal dendrites can be inhibited, and the cycle life and the working performance of the alkali metal battery are improved.
(3) The invention provides a preparation method of electrolyte, which is simple, and the method further ensures that the electrolyte additive and the mixed solvent are uniformly mixed in a magnetic stirring and ultrasonic dispersing mode, ensures the uniformity of mixing the added ionic liquid and the mixed solvent, and avoids concentration polarization caused by concentration gradient in a system. In the application of the battery or the electrode, the formed SEI film can be uniform and compact, so that the battery can have stable long-time circulation and has good electrochemical performance.
(4) The invention provides application of electrolyte, which can uniformly and densely form a film on the surface of an alkali metal electrode body, has certain controllability of film forming conditions, and is characterized in that before electrochemical circulation, an SEI film is prefabricated on the surface of the alkali metal electrode body in advance by pre-reacting the alkali metal electrode body with the electrolyte, so that an alkali metal electrode with the SEI film is obtained, and the electrode is applied to an alkali metal battery, thereby reducing consumption of additive molecules in the circulation process and being more beneficial to the exertion of electrostatic shielding effect of the alkali metal electrode.
(5) The invention provides an alkali metal battery, wherein the alkali metal electrode of the battery is uniform in alkali metal deposition in circulation, growth of alkali metal dendrite is inhibited, so that the safety performance of the battery is improved, the electrochemical performance of the battery can be stably exerted at a high level, the assembled alkali metal symmetrical battery has smaller polarization, and the whole battery has higher coulomb efficiency and capacity retention rate, so that a safe and long-acting alkali metal battery can be obtained, and the cycle life of the battery is favorably and stably prolonged.
Drawings
Fig. 1 is a graph showing the results of the cycle test of the button full cell assembled from the test group electrolyte and the control group electrolyte in test example 1.
Fig. 2 is a charge-discharge voltage-specific capacity curve of the button full cell assembled from the experimental group electrolyte in test example 1 for the first three weeks.
Fig. 3 is a charge-discharge voltage-specific capacity curve of the button full cell assembled from the experimental group electrolyte in test example 2 for the first three weeks.
Detailed Description
The invention will be further described with reference to the following detailed description, wherein the processes are conventional, unless otherwise indicated, and wherein the starting materials are commercially available or prepared from the literature, unless otherwise indicated.
Example 1
A lithium metal battery electrolyte containing tetrafluoroboric acid tetra acetonitrile copper (I) ([ (CH 3CN)4Cu]BF4) additive) and its preparation method are as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, lithium bistrifluoromethylsulfonyl imide (LiTFSI) is added into an organic solvent, and the organic solvent is uniformly mixed to obtain a mixed solvent, wherein the organic solvent consists of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) according to the volume ratio of 1:1, and the use amount of LiTFSI ensures that the concentration of LiTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen content and the water content in the glove box to be less than 1ppm, adding copper (I) tetrafluoroborate [ (CH 3CN)4Cu]BF4) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the purpose of uniform mixing, thereby obtaining a mixed solution, wherein [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1 ], standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1), and the concentration of LiTFSI in the electrolyte is 1mol/L.
Example 2
A lithium metal battery electrolyte containing a copper (I) tetraacetonitrile hexafluorophosphate ([ (CH 3CN)4Cu]PF6) additive, the preparation method of which is as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, liTFSI is added into an organic solvent, and the organic solvent is mixed uniformly to obtain a mixed solvent, wherein the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and the use amount of LiTFSI ensures that the concentration of LiTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen content and the water content in the glove box to be less than 1ppm, adding copper (I) tetra-acetonitrile hexafluorophosphate [ (CH 3CN)4Cu]PF6) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the purpose of uniform mixing, thereby obtaining a mixed solution [ (CH 3CN)4Cu]PF6 concentration is 1mg mL -1 ], standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]PF6 concentration is 1mg mL -1), and the concentration of LiTFSI in the electrolyte is 1mol/L.
Example 3
A lithium metal battery electrolyte containing copper (I) tetrafluoromethane sulfonate ([ (CH 3CN)4Cu]CF3SO3) additive) with the following preparation method:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, liTFSI is added into an organic solvent, and the organic solvent is mixed uniformly to obtain a mixed solvent, wherein the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and the use amount of LiTFSI ensures that the concentration of LiTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen content and the water content in the glove box to be less than 1ppm, adding copper (I) tetraacetonitrile triflate [ (CH 3CN)4Cu]CF3SO3) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the aim of uniform mixing, thereby obtaining a mixed solution, wherein [ (CH 3CN)4Cu]CF3SO3 concentration is 1mg mL -1; and standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]CF3SO3 concentration is 1mg mL -1), and the LiTFSI concentration in the electrolyte is 1mol/L.
Example 4
A lithium metal battery electrolyte containing tetrafluoroboric acid tetra acetonitrile copper (I) ([ (CH 3CN)4Cu]BF4) additive) and its preparation method are as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, liTFSI is added into an organic solvent, and the organic solvent is mixed uniformly to obtain a mixed solvent, wherein the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and the use amount of LiTFSI ensures that the concentration of LiTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen content and the water content in the glove box to be less than 1ppm, adding copper (I) tetrafluoroborate [ (CH 3CN)4Cu]BF4) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the purpose of uniform mixing, thereby obtaining a mixed solution, wherein [ (CH 3CN)4Cu]BF4 concentration is 0.5mg mL -1 ], standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]BF4 concentration is 0.5mg mL -1), and the LiTFSI concentration in the electrolyte is 1mol/L.
Example 5
A lithium metal battery electrolyte containing tetrafluoroboric acid tetra acetonitrile copper (I) ([ (CH 3CN)4Cu]BF4) additive) and its preparation method are as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, liTFSI is added into an organic solvent, and the organic solvent is mixed uniformly to obtain a mixed solvent, wherein the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and the use amount of LiTFSI ensures that the concentration of LiTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen content and the water content in the glove box to be less than 1ppm, adding copper (I) tetrafluoroborate [ (CH 3CN)4Cu]BF4) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the purpose of uniform mixing, thereby obtaining a mixed solution, wherein [ (CH 3CN)4Cu]BF4 concentration is 1.5mg mL -1 ], standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]BF4 concentration is 1.5mg mL -1), and the LiTFSI concentration in the electrolyte is 1mol/L.
Example 6
A lithium metal battery electrolyte containing tetrafluoroboric acid tetra acetonitrile copper (I) ([ (CH 3CN)4Cu]BF4) additive) and its preparation method are as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, liTFSI is added into an organic solvent, and the organic solvent is mixed uniformly to obtain a mixed solvent, wherein the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and the use amount of LiTFSI ensures that the concentration of LiTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen and water content in the glove box to be less than 1ppm, adding copper (I) tetrafluoroborate [ (CH 3CN)4Cu]BF4) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the purpose of uniform mixing, thereby obtaining a mixed solution [ (CH 3CN)4Cu]BF4 concentration is 2mg mL -1 ], standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]BF4 concentration is 2mg mL -1), and the concentration of LiTFSI in the electrolyte is 1mol/L.
Example 7
A lithium metal battery electrolyte containing tetrafluoroboric acid tetra acetonitrile copper (I) ([ (CH 3CN)4Cu]BF4) additive) and its preparation method are as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, liTFSI is added into an organic solvent, and the organic solvent is mixed uniformly to obtain a mixed solvent, wherein the organic solvent consists of 4-methyl-1, 3-dioxolane (4-MeDOL) and DME according to the volume ratio of 1:1, and the use amount of LiTFSI ensures that the concentration of LiTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen content and the water content in the glove box to be less than 1ppm, adding copper (I) tetrafluoroborate [ (CH 3CN)4Cu]BF4) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the purpose of uniform mixing, thereby obtaining a mixed solution, wherein [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1 ], standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1), and the concentration of LiTFSI in the electrolyte is 1mol/L.
Example 8
A lithium metal battery electrolyte containing tetrafluoroboric acid tetra acetonitrile copper (I) ([ (CH 3CN)4Cu]BF4) additive) and its preparation method are as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, liTFSI is added into an organic solvent, and the organic solvent is mixed uniformly to obtain a mixed solvent, wherein the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and the use amount of LiTFSI ensures that the concentration of LiTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the oxygen content and the water content in the glove box to be less than 1ppm, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃, adding copper (I) tetrafluoroborate ([ (CH 3CN)4Cu]BF4) into the mixed solvent, and magnetically stirring for 1h by using a magnetic stirrer to achieve the purpose of uniform mixing, so as to obtain a mixed solution, wherein [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1; and standing for 1h to obtain an electrolyte with [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1), and the LiTFSI concentration in the electrolyte is 1mol/L.
Example 9
A lithium metal electrode with SEI film is prepared by the following steps:
In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, the temperature in the glove box is controlled to be 25 ℃ plus or minus 5 ℃, lithium foil is fully soaked in the electrolyte prepared in the embodiment 1, the lithium metal and the electrolyte are subjected to pre-reaction for 1h, and after the reaction is finished, an SEI film is formed on the surface of the lithium foil in situ, so that the lithium metal electrode with the lithium fluoride-rich SEI film is obtained.
Accordingly, the lithium metal electrode is composed of a lithium foil and an SEI film attached to the lithium foil, which is a lithium fluoride-rich SEI film preformed by adjusting an electrolyte solvation structure by copper (I) tetra-acetonitrile tetrafluoroborate.
Example 10
A lithium metal electrode with SEI film is prepared by the following steps:
In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, the temperature in the glove box is controlled to be 25 ℃ plus or minus 5 ℃, lithium foil is fully soaked in the electrolyte prepared in the embodiment 1, the lithium metal and the electrolyte are subjected to pre-reaction for 0.5h, and after the reaction is finished, an SEI film is formed on the surface of the lithium foil in situ, so that the lithium metal electrode with the lithium fluoride-rich SEI film is obtained.
Accordingly, the lithium metal electrode is composed of a lithium foil and an SEI film attached to the lithium foil, which is a lithium fluoride-rich SEI film preformed by adjusting an electrolyte solvation structure by copper (I) tetra-acetonitrile tetrafluoroborate.
Example 11
A lithium metal electrode with SEI film is prepared by the following steps:
in a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, the temperature in the glove box is controlled to be 60 ℃ plus or minus 5 ℃, lithium foil is fully soaked in the electrolyte prepared in the embodiment 1, the lithium metal and the electrolyte are subjected to pre-reaction for 1h, and after the reaction is finished, an SEI film is formed on the surface of the lithium foil in situ, so that the lithium metal electrode with the lithium fluoride-rich SEI film is obtained.
Accordingly, the lithium metal electrode is composed of a lithium foil and an SEI film attached to the lithium foil, which is a lithium fluoride-rich SEI film preformed by adjusting an electrolyte solvation structure by copper (I) tetra-acetonitrile tetrafluoroborate.
Example 12
A sodium metal battery electrolyte containing tetrafluoroboric acid tetra acetonitrile copper (I) ([ (CH 3CN)4Cu]BF4) additive) and its preparation method are as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, and sodium bistrifluoromethylsulfonyl imide (NaTFSI) is added into an organic solvent, and uniformly mixed to obtain a mixed solvent, wherein the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and the use amount of NaTFSI ensures that the concentration of NaTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen and water content in the glove box to be less than 1ppm, adding copper (I) tetrafluoroborate [ (CH 3CN)4Cu]BF4) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the purpose of uniform mixing, thereby obtaining a mixed solution [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1 ], standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1), and the concentration of NaTFSI in the electrolyte is 1mol/L.
Example 13
A potassium metal battery electrolyte containing tetrafluoroboric acid tetra acetonitrile copper (I) ([ (CH 3CN)4Cu]BF4) additive) and its preparation method are as follows:
(1) In a glove box filled with argon, the oxygen content and the water content in the glove box are both less than 1ppm, potassium bistrifluoromethylsulfonylimide (KTFSI) is added into an organic solvent, and the organic solvent is uniformly mixed to obtain a mixed solvent, wherein the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and the use amount of KTFSI ensures that the concentration of KTFSI in the electrolyte prepared in the embodiment is 1mol/L.
(2) Continuing to carry out the process in the glove box filled with argon, controlling the temperature in the glove box to be 25 ℃ plus or minus 5 ℃ and the oxygen and water content in the glove box to be less than 1ppm, adding copper (I) tetrafluoroborate [ (CH 3CN)4Cu]BF4) into the mixed solvent, magnetically stirring for 1h by using a magnetic stirrer, and ultrasonically dispersing for 1h by using an ultrasonic dispersing instrument to achieve the purpose of uniform mixing, thereby obtaining a mixed solution, wherein [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1 ], standing for 1h to obtain an electrolyte [ (CH 3CN)4Cu]BF4 concentration is 1mg mL -1), and the KTFSI concentration in the electrolyte is 1mol/L.
Test example 1
The electrolyte prepared in example 1 was assembled with a lithium metal negative electrode, liFePO 4 positive electrode to form a button full cell (noted as experimental group);
The button full battery (recorded as a control group) is formed by assembling a commercial common ether-based electrolyte with a lithium metal negative electrode and a LiFePO 4 positive electrode, wherein the commercial common ether-based electrolyte consists of an organic solvent, liTFSI electrolyte lithium salt and LiNO 3 additive, the organic solvent consists of DOL and DME according to the volume ratio of 1:1, and in the commercial common ether-based electrolyte, the concentration of LiTFSI is 1mol/L, and the mass fraction of LiNO 3 is 1%.
The button full battery of the experimental group and the control group is assembled by sequentially adopting a positive electrode shell, a positive electrode plate, 30 mu L of electrolyte, a diaphragm, 30 mu L of electrolyte, a lithium plate, a stainless steel gasket and a negative electrode shell, and pressing the battery by using a punching machine after the assembly is completed. The charge and discharge test was performed at a rate of 1C (1c=170 mAh g -1), the test results obtained are shown in fig. 1, and the first three week voltage-specific capacity curve of the experimental group is shown in fig. 2.
As can be seen from fig. 1, the full cells of the control group exhibited a higher initial capacity, which was close to the limiting specific capacity, but the capacity decreased rapidly in the subsequent cycles, and exhibited a specific capacity of only about 130mAh g -1 by the 60 th week, and the coulomb efficiency was also unstable and fluctuated greatly. However, the experimental group full cell assembled using the electrolyte prepared in example 1, although the initial capacity was slightly lower than that of the control group full cell, showed no significant decrease in capacity during the 60-week cycle, and the coulombic efficiency was also overall stable.
As can be seen from fig. 2, the discharge plateau of the battery prepared in the experimental group is a high voltage of 3.35V, the plateau is long and stable, and the specific discharge capacity is kept around 160mAh g -1, which is close to the theoretical capacity thereof, after undergoing the first week of irreversible film forming reaction.
In addition, the scanning electron microscope is adopted to characterize lithium cathodes in the lithium metal batteries of the experiment group and the control group after circulation, and test results show that the lithium metal battery of the experiment group has a remarkable effect of inhibiting dendrite growth compared with the lithium metal battery of the control group.
Therefore, it is known from the above test results that the electrolyte prepared in example 1 can form a LiF-rich SEI film by controlling the electrolyte solvation structure through Cu +, thereby effectively suppressing the generation of lithium dendrites and "dead lithium", avoiding capacity degradation of lithium metal batteries, and exhibiting excellent electrochemical properties.
Test example 2
The electrolyte prepared in example 4 was assembled with a lithium metal negative electrode and a LiFePO 4 positive electrode to form a button full battery, and the assembly sequence of the full battery was that a positive electrode case, a positive electrode sheet, 30 μl of electrolyte, a separator, 30 μl of electrolyte, a lithium sheet, a stainless steel gasket and a negative electrode case were sequentially assembled, and the battery was compressed by a punching machine after the assembly was completed. The charge and discharge test was performed at a rate of 1C (1c=170 mAh g -1), and the first three weeks voltage-specific capacity curve (excluding the first week cycle) of the full cell is shown in fig. 3.
As can be seen from fig. 3, the battery also has a long and stable high-voltage discharge platform with a voltage of 3.35V, and after undergoing the first week irreversible film forming reaction, the discharge specific capacity is about 160mAh g -1, which is relatively close to the theoretical capacity.
In addition, a scanning electron microscope is adopted to characterize a lithium cathode in the battery after circulation, and test results show that the battery has a remarkable effect of inhibiting growth of lithium dendrites.
Thus, it is apparent from the above test results that the electrolyte additive introduced into the electrolyte prepared in example 4 shows inhibition of lithium dendrite growth, so that the assembled battery can show better electrochemical performance.
The electrolyte or the alkali metal electrode of the alkali metal cell provided by other examples with reference to the above method shows the inhibition effect on dendrite growth, higher discharge capacity and better cycle stability, and improved coulombic efficiency compared with the unmodified electrolyte or electrode, so the effect of the additive for electrolyte solvation structure regulation based on cuprous ions provided by tetra-acetonitrile copper (I) salt, which is proposed by the invention, on the improvement of SEI film performance and the significant effect of inhibition on dendrite growth of the alkali metal cell are further illustrated.
The invention includes, but is not limited to, the above embodiments, any equivalent or partial modification made under the principle of the spirit of the invention, shall be considered as being within the scope of the invention.
Claims (8)
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