CN115036468A - Sodium ion battery electrode material pre SEI film hard carbon material and application thereof - Google Patents
Sodium ion battery electrode material pre SEI film hard carbon material and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 74
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 35
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 29
- 239000007772 electrode material Substances 0.000 title claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 47
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 22
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 22
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000012905 visible particle Substances 0.000 claims abstract 2
- 239000011734 sodium Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000007784 solid electrolyte Substances 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000016507 interphase Effects 0.000 claims description 2
- -1 LITFSI Inorganic materials 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- 229910013188 LiBOB Inorganic materials 0.000 claims 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims 1
- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- 229910001290 LiPF6 Inorganic materials 0.000 claims 1
- 229910019398 NaPF6 Inorganic materials 0.000 claims 1
- 239000006258 conductive agent Substances 0.000 claims 1
- PWRLWCQANJNXOR-UHFFFAOYSA-N dilithium chloro(dioxido)borane Chemical compound [Li+].[Li+].[O-]B([O-])Cl PWRLWCQANJNXOR-UHFFFAOYSA-N 0.000 claims 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 229910001545 sodium hexafluoroantimonate(V) Inorganic materials 0.000 claims 1
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 claims 1
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims 1
- 238000003828 vacuum filtration Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 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 18
- 229910052708 sodium Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 3
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparation method and application of a sodium ion battery electrode material pre-SEI film hard carbon material, wherein lithium salt and sodium salt are added into a heated organic solvent while stirring, and the stirring is continued until a uniform dispersion liquid without visible particles is obtained; and adding a hard carbon powder material into the dispersion liquid, and stirring for reaction for a preset time according to the set stirring speed, the set heating temperature and the set stirring reaction time to obtain the pre-SEI hard carbon material. And then removing the residual organic solvent on the surface through filtration, washing and calcination. The material of the invention has the characteristics of low investment, simple preparation process flow, easy industrial production, high product consistency, easy adjustment of the degree of SEI film pre-formation of the product and the like. In addition, the invention adopts the optimized negative plate formula and structural design, so that the sodium ion battery has the characteristic of low internal resistance, can be charged and discharged with large current, has good cycle performance and high first charging and discharging efficiency, and can be particularly used as a power supply for large-multiplying-power electric tools, garden tools and the like.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a hard carbon anode material for pre-sodium treatment of a sodium ion battery anode material and application thereof.
Background
In recent years, sodium ion batteries, which are similar to lithium ion batteries, have attracted considerable attention in recent years due to their low cost, fast ion conductivity in the electrolyte and low standard redox potential (-2.71V versus standard electrode potential) close to that of lithium. In sodium ion batteries, a large number of organic compounds besides inorganic compounds can be used as negative electrode materials to be researched, but hard carbon becomes the most promising negative electrode material for high-performance sodium ion batteries due to the advantages of high specific capacity, voltage plateau, low cost and the like. In 2000, Dahn et al reported that glucose pyrolytic hard carbon was used as a negative electrode material of a sodium ion battery for the first time, and found that the material has a reversible specific capacity of more than 300 mA · h/g, which is far superior to that of graphite and soft carbon materials. However, the most important disadvantage of hard carbon as the negative electrode material of sodium ion batteries is that the hard carbon has a large irreversible capacity, so that a large amount of sodium ions are consumed in the first charging process.
In order to compensate for the irreversible capacity of the negative electrode, the hard carbon material may be pre-sei (solid Electrolyte interface) formed. The SEI film can prevent organic solvent from entering gaps among the carbon lattice layers, can effectively inhibit poor phenomena such as stripping of electrolyte solvent on the surface structure of hard carbon, electrochemical oxidation and the like, and improves the stability and the cycle reversibility of the carbon structure. The current method for pre-sodium treatment of the negative electrode mainly comprises the following steps: electrochemical methods, direct contact methods, soaking methods in sodium-containing organic solutions, and the like. In patent CN201710540148.8, southwest university discloses a direct contact method, in which Na metal is directly extruded on the surface of a negative electrode, the operation is complicated, the requirement on the process level of raw materials is high, and there is a limitation that commercialization is difficult to achieve, as with the electrochemical method. Therefore, the development and optimization of the simple and feasible sodium pre-intercalation process method have important practical significance for preparing the hard carbon sodium ion battery cathode material with high cycle capacity and rate capability. In patent CN202011473686.8, the university of fertilizer mixing industry adopts two solutions (sodium-containing solution + organic solvent) soaking method to pre-sodium the negative plate, so that the cycle life and initial coulomb efficiency of the sodium ion battery are both significantly improved. Luwei et al of Shenzhen International institute of study at Qinghua university in patent CN113178548A show that they prepared the excellent rate capability and ICE of more than 96.8% of the pre-sodium graphene negative electrode piece in the sodium ion battery, and again confirmed the feasibility of the sodium-containing solution soaking method.
However, hard carbon and pre-lithiated hard carbon, which act as SEI films with lithium and sodium co-used in sodium ion batteries, have not been discussed.
Disclosure of Invention
The invention aims to provide a method for improving the impedance, the cycle performance and the first effect of a sodium-ion battery. The irreversible loss of the sodium part in the later cycle process of the sodium-ion battery can be reduced by soaking the hard carbon negative electrode powder material in organic or inorganic sodium-containing and lithium salt solution for pre-SEI.
The purpose of the invention can be realized by the following technical scheme:
a sodium-embedded hard carbon for an electrode material of a sodium ion battery comprises the following preparation processes: adding lithium salt and sodium salt into a heated organic solvent while stirring, and stirring and dispersing; and adding a hard carbon powder material into the dispersion liquid, and stirring for reaction for a preset time according to the set stirring speed, the set heating temperature and the set stirring reaction time to obtain the pre-SEI (solid electrolyte interphase) filmed hard carbon material. And then removing the residual organic solvent on the surface by filtering, washing and calcining.
A sodium-pre-embedded hard carbon for an electrode material of a sodium ion battery comprises the following preparation processes: adding the lithium salt and the sodium salt into heated silicone oil or oil amine solvent while stirring, and stirring and dispersing; adding a hard carbon powder material with the particle size of 5-60 mu m into the dispersion liquid, wherein the molar ratio of the hard carbon to the mixed salt of lithium salt and sodium salt is 1: 2-10; the concentration of the prepared dispersion liquid is 1-50 g/L. And according to the set stirring speed of 150-600 rpm, the heating temperature of 60-150 ℃ and the stirring reaction preset time of 15 min-4 h, obtaining the SEI pre-filmed hard carbon material. And after filtering, washing and filtering the mixture for 3 times by using normal hexane and absolute ethyl alcohol, and calcining the pre-SEI filmed hard carbon material for 1.5 to 8 hours at 200-500 ℃ in an inert atmosphere after drying.
More preferably, the molar ratio of the hard carbon to the mixed salt of the lithium salt and the sodium salt is 1: 4-8. When the molar ratio of the hard carbon to the mixed salt of the lithium salt and the sodium salt is less than 1:2, the concentration of the lithium salt and the sodium salt is low, a formed SEI film is not compact enough, the improvement effect is not obvious, and when the ratio of the raw materials exceeds 1:10, the cost is increased;
further preferably, the stirring speed is set to 250 to 400 rpm. The stirring speed influences the dispersion degree, and then influences the uniformity of an SEI film on the surface of hard carbon, and when the stirring speed is less than 150rpm, the hard carbon powder is not well dispersed;
more preferably, the heating temperature is set to be between 80 and 120 ℃. The heating temperature influences the reaction rate, the high temperature can reduce the viscosity of the organic solvent, further improve the reaction rate and reduce the reaction time;
further preferably, the stirring reaction is set for 20 min-1 h. The length of the stirring reaction affects the extent of the reaction, and sufficient reaction time facilitates the formation of a complete and robust solid electrolyte interfacial film.
The invention has the beneficial effects that:
1) the composite salt pre-SEI film-coated hard carbon powder material can regulate the pre-SEI degree through various influence factors such as raw material proportion, stirring speed, heating temperature, stirring reaction time and the like. Sufficient lithium salt (1: 4-8), proper stirring speed (250-400 rpm), proper heating temperature (80-120 ℃), and sufficient reaction time (20 min-1 h) are favorable for generating an orderly, compact and uniform SEI film. When the molar ratio of the hard carbon to the mixed salt of the lithium salt and the sodium salt is less than 1:2, the concentration of the lithium salt and the sodium salt is low, the formed SEI film is not compact enough, and the improvement effect is not obvious; the stirring speed influences the dispersion degree, and then influences the uniformity of an SEI film on the surface of hard carbon, and when the stirring speed is less than 150rpm, the hard carbon powder is not well dispersed; the heating temperature influences the reaction rate, and the high temperature can reduce the viscosity of the organic solvent and further improve the reaction rate; the length of the stirring reaction affects the extent of the reaction, and sufficient reaction time facilitates the formation of a complete and robust solid electrolyte interfacial film.
2) When the synthesized pre-lithiation/pre-sodium treatment/pre-lithiation & sodium treatment hard carbon is applied to a sodium ion battery, the SEI film with ordered pores reduces the ion migration resistance, so that lithium ions can be rapidly diffused to the surface of the hard carbon and reduced and embedded into a hard carbon sheet layer, and the ionic conductivity of the system is improved; meanwhile, the continuous consumption of the electrolyte and the positive active sodium salt in the subsequent circulation process is compensated, and the adverse phenomena of stripping of an electrolyte solvent on a hard carbon surface structure, electrochemical oxidation and the like can be effectively inhibited, so that the sodium ion battery has the excellent effects of low impedance, high circulation retention rate and first effect improvement.
3) Compared with the previous pre-sodium treatment research, the preparation method is simpler, more diversified and more economic, and is easy to realize scale production.
The method for pre-SEI treatment of the hard carbon cathode material of the sodium ion battery can enable the sodium ion battery to have low internal impedance characteristics, and can effectively improve the cycle performance and the first effect of the sodium ion battery. In addition, the obtained pre-lithiation/sodium-modified hard carbon material has high consistency, and the pre-SEI film formation degree of the product is easy to adjust. In addition, the method has simple preparation process flow and is easy to realize industrial production.
Drawings
Fig. 1 is a graph comparing EIS of pre-SEI hard carbon materials prepared in example 1 and comparative example 2 with untreated hard carbon materials.
Fig. 2 is a graph of rate performance at different electric current densities for a sodium ion battery having the pre-sodiumized hard carbon material as the negative active ingredient prepared in example 1, and compares sodium ion batteries having non-pre-sodiumized hard carbon material as the negative active ingredient.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
And (3) electrochemical performance testing:
the prelithiation/pre-sodium hard carbon synthesized by the method, the acetylene black and the binder carboxymethyl cellulose sodium (CMC) are uniformly mixed according to the mass ratio of 85:5:10, coated on a copper foil, dried in vacuum at 80 ℃ overnight, and then punched into an electrode slice, wherein the standard areal density range is 10-12 mg cm < -2 >.
Taking metal sodium as a counter electrode, and dissolving the metal sodium into the solution with a volume ratio of 1.0 mol/L: 1 of Ethylene Carbonate (EC)/diethyl carbonate (DEC) in a mixed solution of NaClO 4 The saline solution is used as electrolyte, the Whatman GF/C glass fiber membrane is used as a diaphragm, the aperture of the Whatman GF/C glass fiber membrane is 1.2 mu m, the thickness of the Whatman GF/C glass fiber membrane is 260 mu m, the foamed nickel is used as a supporting conductive device, and the button cell is assembled in an argon glove box.
The new MIHW-200-160CH type battery tester is adopted to perform the performance tests such as electrochemical charge-discharge circulation and the like, and the charge-discharge voltage range is 0.01V-2.0V (vs. Na) + Na), the charging and discharging currents are respectively 50mA and 100mA when the battery is circulated, and the test temperature is 25 ℃.
A VSP multi-channel electrochemical workstation produced by France (Bio-Logic company) is selected for carrying out the AC impedance test of the button half-cell, the range of the frequency signal is 0.01Hz-100KHz, the amplitude of the AC signal adopted by the test is 5mV, and the experimental temperature is 25 ℃. The basic principle is as follows: by applying a small amplitude alternating perturbation potential wave with frequency variation, the ratio of the alternating potential to the generated alternating signal is measured as a function of the sine wave frequency omega, and the properties of electrode material dynamics, ion diffusion and the like can be analyzed accordingly.
The following examples and comparative examples all adopt the above-mentioned buckling method and test method, and the materials used are consistent with the assembly conditions, test conditions, and the like.
Example 1
Adding 5g of LiCl and 5g of NaCl serving as lithium salt into 500ml of silicone oil heated to 60 ℃ while stirring, and stirring and dispersing; adding hard carbon powder material with the particle size of about 10 mu m into the dispersion, wherein the molar ratio of the hard carbon to the mixed salt of lithium salt and sodium salt is 1: 6. Setting the stirring speed at 300 rpm, the heating temperature at 80 ℃ and the stirring reaction time to be 20min to obtain the SEI pre-filmed hard carbon material. After filtration, the mixture was washed and filtered 3 times with n-hexane and absolute ethanol. After drying, calcining for 2h at 400 ℃ in a nitrogen atmosphere to remove the residual organic solvent on the surface.
Example 2
Adding 10g of lithium salt 4-phenyl lithium borate into 500ml of oleylamine solvent heated to 60 ℃ while stirring, and stirring and dispersing; adding hard carbon powder material with the particle size of about 10 mu m into the dispersion liquid, wherein the molar ratio of the hard carbon to the mixed salt of the lithium salt and the sodium salt is 1: 6. And stirring at 300 rpm, heating at 80 deg.C and stirring for 20min to obtain the SEI-precoated hard carbon material. After filtration, the mixture was washed and filtered 3 times with n-hexane and absolute ethanol. After drying, calcining for 2h at 400 ℃ in a nitrogen atmosphere to remove the residual organic solvent on the surface.
Example 3
Adding 5g LiCl of lithium salt and 5g NaCl of sodium salt into 500ml of oleylamine solvent heated to 60 ℃ while stirring, and stirring and dispersing; adding hard carbon powder material with the particle size of about 10 mu m into the dispersion, wherein the molar ratio of the hard carbon to the mixed salt of lithium salt and sodium salt is 1: 6. Setting the stirring speed at 300 rpm, the heating temperature at 80 ℃ and the stirring reaction time to be 20min to obtain the SEI pre-filmed hard carbon material. After filtration, the mixture was washed and filtered 3 times with n-hexane and absolute ethanol. After drying, calcining for 2h at 400 ℃ in a nitrogen atmosphere to remove the residual organic solvent on the surface.
Example 4
Adding 20g of lithium salt 4-phenyl lithium borate into 500ml of oleylamine solvent heated to 90 ℃ while stirring, and stirring and dispersing; adding hard carbon powder material with the particle size of 10 mu m into the dispersion liquid, wherein the molar ratio of the hard carbon to the mixed salt of lithium salt and sodium salt is 1: 10. And stirring at 400 rpm, heating at 90 deg.c and stirring for 1 hr to obtain the pre-SEI filming hard carbon material. After filtration, the mixture was washed and filtered 3 times with n-hexane and absolute ethanol. After drying, calcining for 2h at 400 ℃ in a nitrogen atmosphere to remove the residual organic solvent on the surface.
Comparative example 1
Consistent with example 1, the only difference was that the lithium, sodium complex salt was replaced with 10g NaCl.
Comparative example 2
The hard carbon material without pretreatment is uniformly mixed with acetylene black, CMC and the like according to the mass ratio of 85:5:10, the mixture is coated on copper foil to prepare a negative plate, and other operations and test methods are consistent with those of the experimental example 1.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
As can be seen from fig. 1, the radius of curvature of the circular arc segment of the pre-lithium, sodium-modified button half cell prepared in example 1 is smaller than that of comparative example 2, indicating that the charge transfer resistance of the pre-sodium-modified negative cell in example 1 is lower than that of the non-pre SEI negative general cell in comparative example 2, which is related to the hard carbon surface treated by pre-SEI having a layer of irreversible solid electrolyte interface film. The SEI film with ordered pores reduces the ion migration resistance, so that lithium ions can be rapidly diffused to the surface of hard carbon and reduced and embedded into a hard carbon layer, and the ionic conductivity of the system is improved; the low frequency regions of both impedance spectra show a diagonal straight line, indicating that charge transfer and transport in the different negative electrode materials of example 1 and comparative example 2 are affected by the diffusion impedance of sodium ions.
As can be seen from the comparative graph of the rate performance test of fig. 2, the rate performance of the pre-SEI battery in example 1 is greatly improved, which indicates that the pre-formed SEI film makes the interface of the pre-sodium salt battery more stable and the rate performance is optimized.
Table 1 is a comparison graph of the first effect of the hard carbon material prepared in each example. As can be seen from table 1, the first coulombic efficiency of the hard carbon battery was increased from 70% to 86% by the pre-SEI treatment, indicating that the pre-SEI treatment successfully suppresses irreversible decomposition and other side reactions of the electrolyte during the first cycle. Moreover, the corresponding cycle performance of the hard carbon subjected to the treatment of the pre-SEI film is also obviously improved, and the capacity retention rate can reach 73% -76% after 200 circles of charging and discharging, and the reason is presumed that the surface of the hard carbon subjected to the pre-SEI film is more stable, the condition of the rupture regeneration of the SEI film in the subsequent cycle process is reduced, and the lithium loss in the long cycle process is effectively avoided.
Table 1:
Claims (8)
1. a hard carbon material of a pre SEI film of an electrode material of a sodium-ion battery is characterized in that: the preparation method comprises the following steps: adding lithium salt and sodium salt into a heated organic solvent while stirring, and continuously stirring until a uniform dispersion liquid without visible particles is obtained; adding a hard carbon powder material into the dispersion, obtaining a pre-SEI (solid electrolyte interphase) filmed hard carbon material according to the set stirring speed, heating temperature and stirring reaction for a preset time, and removing the organic solvent remained on the surface by filtering, washing and calcining.
2. The sodium-ion battery electrode material pre SEI film hard carbon material as set forth in claim 1, wherein: the organic solvent is one or a mixture of more of silicone oil, oleylamine and NMP.
3. The sodium-ion battery electrode material pre SEI film hard carbon material as set forth in claim 1, wherein: wherein the lithium salt is one or a mixture of more of LiCl, LiBr, LiI, LiClO4, LiBF4, LiPF6, LiAsF6, LiFSI, LITFSI, LiCF3SO3, LiN (C2F5SO2)2, LiC (CF3SO2)3, LiN (CF3SO2)2, LiBOB, lithium chloroborate, lithium lower aliphatic carboxylate and lithium 4-phenylboronate.
4. The method for pre-SEI film formation of a negative electrode as claimed in claim 1, wherein the sodium salt comprises one of NaPF6, NaClO4, NaBF4, NaNO3, NaAsF6, NaCF3CO2, NaSbF6, NaC6HsCO2, Na (CH3) C6H4SO3, NaHSO4, NaB (C6Hs)4 or a mixture of two or more thereof.
5. The sodium-ion battery electrode material pre SEI film hard carbon material as set forth in claim 1, wherein: the stirring speed is in the range of 150-600 rpm; the heating temperature is between 60 and 150 ℃; the stirring reaction time is 15 min-4 h.
6. The sodium-ion battery electrode material pre SEI film hard carbon material as set forth in claim 1, wherein: the particle size of the hard carbon material is in the range of 5-60 mu m; the molar ratio of the hard carbon to the mixed salt of the lithium salt and the sodium salt is 1: 2-10; the concentration of the prepared dispersion liquid is 1-50 g/L.
7. The sodium-ion battery electrode material pre SEI film hard carbon material as set forth in claim 1, wherein: the filtering mode is 200 meshes of screen mesh or vacuum filtration by using a vacuum filter; the washing solvent is n-hexane and ethanol, and the calcining atmosphere is argon, nitrogen or the mixture of the two; the sintering temperature is in the range of 200-500 ℃; the calcination time is 1.5-8 h.
8. The electrode material pre SEI film hard carbon material for the sodium-ion battery and the application thereof as claimed in claim 1, wherein the sodium-ion battery is composed of a working electrode, a counter electrode, an electrolyte and a diaphragm, and the working electrode material is a mixture composed of the pre SEI film negative electrode active material as claimed in claim 1, a conductive agent and a binder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105948108A (en) * | 2016-04-29 | 2016-09-21 | 宁波大学 | Sodium lithium titanate nanowire and preparation method thereof |
| CN106229512A (en) * | 2016-08-12 | 2016-12-14 | 中南大学 | A kind of battery preparation method of 3-D ordered multiporous silicate/C composite |
| US20180351200A1 (en) * | 2017-05-30 | 2018-12-06 | Nanotek Instruments, Inc. | Shape-Conformable Alkali Metal Battery Having a Conductive and Deformable Quasi-solid Polymer Electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948108A (en) * | 2016-04-29 | 2016-09-21 | 宁波大学 | Sodium lithium titanate nanowire and preparation method thereof |
| CN106229512A (en) * | 2016-08-12 | 2016-12-14 | 中南大学 | A kind of battery preparation method of 3-D ordered multiporous silicate/C composite |
| US20180351200A1 (en) * | 2017-05-30 | 2018-12-06 | Nanotek Instruments, Inc. | Shape-Conformable Alkali Metal Battery Having a Conductive and Deformable Quasi-solid Polymer Electrode |
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