CN114497500A - Nano tin/hard carbon composite electrode material for sodium ion battery and preparation method thereof - Google Patents
Nano tin/hard carbon composite electrode material for sodium ion battery and preparation method thereof Download PDFInfo
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 65
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 47
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 26
- 229920005610 lignin Polymers 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 235000019357 lignosulphonate Nutrition 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 55
- 239000013078 crystal Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 150000001722 carbon compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000002733 tin-carbon composite material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910004751 Na15Sn4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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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Abstract
The invention discloses a preparation method of a nano tin/hard carbon composite electrode material for a sodium ion battery, which comprises the following steps: dispersing or dissolving lignin, an inorganic tin compound and a surfactant in water, and carrying out hydrothermal reaction at a certain temperature and for a certain time to obtain a tin oxide/hydrothermal carbon composite precipitate; and (3) pyrolyzing the precipitate at high temperature after washing and drying, and then performing ball milling, washing and drying to obtain the nano tin/hard carbon composite electrode material. The electrode material disclosed by the invention has the characteristics of high rate performance, long cycle stability and the like, and is a novel energy storage sodium ion battery cathode material which is green, environment-friendly and low in price. The preparation method is simple and easy to operate, and the used raw material lignin is widely distributed and renewable in nature.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a nano tin/hard carbon composite electrode material for a sodium ion battery and a preparation method thereof.
Background
Lithium ion batteries are considered one of the most promising energy storage devices due to their high energy density and good cycling stability. However, the severe shortage and high cost of lithium resources limit the sustainable development of lithium ion batteries. Therefore, developing new energy storage systems that are cost effective and high performance remains a challenge in this area. Sodium and lithium have similar physicochemical properties, and the storage capacity of sodium element in earth crust is very rich and far higher than that of lithium, and the production processes of sodium ion batteries and lithium ion batteries are communicated, so the sodium ion batteries are considered as candidates most possibly replacing the lithium ion batteries.
The development of negative electrode materials of sodium ion batteries has been a technical difficulty for commercialization of the sodium ion batteries, because the radius of sodium ions is much larger than that of lithium ions, which makes it impossible to simply apply the negative electrode materials of high-performance lithium ion batteries directly to the sodium ion batteries. Heretofore, sodium ion battery negative electrode materials mainly include carbonaceous materials, metals (such as Sn, Sb, Ge), metal oxides, and the like. Of these, metallic Sn materials are of interest, which can form an alloy Na with Na15Sn4The theoretical capacity is up to 837 mAh/g. However, the huge volume expansion effect of pure Sn electrodes leads to structural failure and very poor cycling performance. In order to solve the problem, Sn is compounded with materials such as carbon, phosphorus, sulfur and the like, so that spontaneous agglomeration of Sn particles can be effectively prevented, and the volume expansion effect of Sn in the cyclic charge-discharge process is relieved. The carbon material can be used as a good carrier due to good conductivity and excellent mechanical properties, so that the volume expansion of Sn is relieved, and the electronic conductivity of the whole material can be improved. Pan et al use polymethyl methacrylate as a precursor, embed Sn nanoparticles into a carbon skeleton by a pyrolytic reduction method, and have a specific discharge capacity of 674mAh/g at a current density of 50mA/g, but have poor cycle performance, and the capacity retention rate of 50 cycles of cycling is reduced to 78% at 50mA/g (Mater Lett.2020, 273, 127909). Li et al prepared a HDN-C @ Sn/G composite of double-layer coated Sn nanoparticles by using dopamine hydrochloride and graphene in combination with hydrothermal and multi-step pyrolysis methods, and the compositeAlthough the strategy effectively relieves the problem of volume expansion of Sn in the process of sodium intercalation, the specific discharge capacity is 466mAh/g under the current density of 200mA/g, and the capacity retention rate is 73% after 1000 cycles of circulation under the large current density of 1A/g, the used carbon source is a petrochemical product, the raw material is expensive, the environmental pollution is easily caused, and the requirement on equipment is high (Nano Lett.2020, 20, 2034 + 2046). Ruan et al, by hydrothermal method, coat the hexamethylene on tin oxide particles, disperse the tin oxide particles on the carbon nanotubes obtained by pyrolysis of polypyrrole, and pyrolyze and reduce the tin oxide particles to obtain a carbon-coated Sn @ N doped carbon nanotube composite, wherein the discharge specific capacity of the electrode is 378mAh/g under the current density of 100mA/g, but the capacity retention rate is only 67% after 150 cycles under the current density of 100mA/g, the cycle performance is still poor, the raw material cost is high, and the large-scale production of the electrode is limited (ACS applied Mater Interfaces 2017, 9(43), 37682-37693). Therefore, in the prior art, a carbon material is used as a carrier to realize the nano dispersion of Sn and relieve the volume expansion of tin in the charging and discharging processes, and a petroleum-based product is used as a precursor of the carbon carrier, so that the cost is high, the crystal face spacing of the carbon carrier is small (about 0.35nm), and the prepared tin-carbon composite electrode has poor cycle stability.
Disclosure of Invention
In view of the above, one of the purposes of the present invention is to provide a nano tin/hard carbon composite electrode material for a sodium ion battery, the negative electrode material has high rate performance and long cycle stability, and the coulombic efficiency is close to 100%, so as to solve the problems of low specific capacity and poor cycle stability of the tin-carbon composite material in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a nano tin/hard carbon composite electrode material for a sodium ion battery comprises the following steps:
(1) dispersing or dissolving lignin, inorganic tin compound and surfactant in water, and stirring to obtain uniform dispersion liquid;
(2) placing the dispersion liquid obtained in the step (1) in a hydrothermal kettle to perform hydrothermal reaction under certain conditions to obtain a tin oxide/hydrothermal carbon composite precipitate;
(3) washing and drying the tin oxide/hydrothermal carbon composite precipitate obtained in the step (2), and pyrolyzing the tin oxide/hydrothermal carbon composite precipitate at high temperature in a tubular furnace under inert atmosphere to obtain a nano tin/hard carbon composite;
(4) and (4) carrying out ball milling, washing and drying on the nano tin/hard carbon composite obtained in the step (3) to obtain the nano tin/hard carbon composite electrode material for the sodium ion battery.
Further, the lignin in the step (1) comprises one or more of enzymatic hydrolysis lignin, alkali lignin, organic solvent lignin, sulfonated lignin and lignosulfonate; the inorganic tin compound comprises one or more of stannous chloride dihydrate, stannic chloride pentahydrate, stannous chloride anhydrate and stannic chloride pentahydrate.
Further, in the step (1), the surfactant includes one or more of polyvinylpyrrolidone and ammonium dihydrogen phosphate, and the water is at least deionized water.
Furthermore, the mass ratio of the lignin, the inorganic tin compound, the surfactant and the water in the step (1) is 1: 0.1-3: 10-80.
Further, the hydrothermal carbonization temperature in the step (2) is 150-300 ℃, the reaction time is 1-48 h, and the filling degree of the hydrothermal kettle is 30-90%.
Further, the washing solvent in the step (3) is deionized water or absolute ethyl alcohol, the drying temperature is 60-150 ℃, and the drying time is 1-36 hours.
Further, in the step (3), the high-temperature pyrolysis temperature is 600-1600 ℃, the pyrolysis time is 0.5-24 h, the heating rate is 1-20 ℃/min, and the inert gas is N2One of Ar and He, and the flow rate of the inert gas is 5-200 sccm.
Further, in the step (4), the rotation speed of ball milling is 100-1200 rpm, the ball milling time is 0.5-10 h, and the particle size after ball milling is 2-10 μm. In order to remove impurities, dilute hydrochloric acid or dilute sulfuric acid water solution is used for washing, the concentration is 0.1-1 mol/L, then deionized water and ethanol are used for alternately centrifuging to be neutral, and finally the nano tin/hard carbon composite material is obtained through drying, wherein the drying temperature is 60-150 ℃, and the drying time is 1-36 hours.
The invention also relates to a nano tin/hard carbon composite electrode material for the sodium ion battery, which is prepared by the preparation method of the nano tin/hard carbon composite electrode material for the sodium ion battery, wherein the carbon content of the negative electrode material is 10-90 wt%.
The invention also relates to a sodium ion battery with the electrode material of the nano tin/hard carbon composite electrode material for the sodium ion battery.
The reaction mechanism existing in the above-disclosed production method is as follows: tin salt and lignin generate a tin oxide/hydrothermal carbon compound through a first step of hydrothermal reaction, so that uniform adhesion of tin oxide on the surface of hydrothermal carbon is realized, and a surfactant in a reaction liquid limits the growth of tin oxide particles; in the second step of pyrolysis, tin oxide and hydrothermal carbon are subjected to redox reaction at high temperature, the tin oxide is directly reduced into metal nano tin by the carbon, and the uniform dispersion of nano tin particles on the surface of the carbon carrier is realized.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) according to the invention, hydrothermal carbon obtained by carbonizing lignin is directly used as a stable carbon carrier, so that the aggregation effect of tin oxide particles is reduced; the hydrothermal carbon reduces tin oxide at high temperature, so that uniform dispersion of nano Sn particles on the surface of a carbon carrier is realized, and the carbon carrier releases stress, thereby effectively relieving volume expansion of Sn in the charging and discharging processes during circulation and maintaining the integrity of an electrode material; the hard carbon in the prepared tin-carbon composite material has good conductivity, and is beneficial to rapid electron transmission; therefore, the nano tin/hard carbon composite electrode material disclosed by the invention has high rate performance and good cycle stability;
(2) according to the invention, biomass lignin is selected as a precursor for preparing the carbon carrier, so that waste is changed into valuable, and the raw material cost is low, green and environment-friendly and renewable;
(3) the tin/hard carbon composite prepared by the simple and controllable hydrothermal and pyrolysis two-step method has a large specific surface area and a porous structure, is favorable for wetting electrolyte, and shortens the diffusion distance of sodium ions; the hard carbon carrier obtained by further pyrolyzing the hydrothermal carbon has a stable structure, good mechanical property and large interplanar spacing (greater than 0.37nm), and can provide additional sodium-embedded active sites, so that the sodium storage characteristic of the tin/hard carbon composite electrode is regulated, controlled and optimized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an XRD pattern of the product obtained in example 1;
FIG. 2 is an SEM photograph of the product obtained in example 1;
FIG. 3 is an XRD pattern of the product obtained in example 2;
FIG. 4 is an SEM photograph of the product obtained in example 2;
FIG. 5 is an XRD pattern of the product obtained in example 3;
FIG. 6 is an SEM photograph of the product obtained in example 3;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a nano tin/hard carbon composite electrode material for a sodium ion battery, which comprises the following steps of:
(1) x-ray diffraction (XRD) test:
the test was carried out using an X-ray powder diffractometer of Rigaku-D/max-2550pc type from Hitachi, Japan, using Cu-Ka as radiation source and a wavelength of
A Ni filter plate is adopted, the pipe flow is 40mA, the pipe pressure is 40KV, the scanning range is 10-90 degrees, the scanning speed is 20 degrees/min, and the step length is 0.08 degrees. Placing the material into a glass slide, flattening, embedding the glass slide into the center of an instrument experiment groove, and testing; phase identification and crystal structure information were analyzed by the JADE5.0 software.
(2) Scanning electron microscopy characterization:
the morphology of the electrode material of the sodium-ion battery prepared in each example was observed with a scanning electron microscope tester model S-4800 manufactured by HITACHI corporation at an acceleration voltage of 5 KV.
Example 1
The embodiment comprises the following specific steps:
(1) weighing 1g of alkali lignin and 0.12g of stannous chloride dihydrate (SnCl)2 2H2O), 0.12g of polyvinylpyrrolidone is added into 50ml of distilled water and stirred uniformly, and then the dispersion is transferred to a hydrothermal kettle to react for 24 hours at 180 ℃ to obtain tin oxide/hydrothermal carbon composite precipitate;
(2) washing the precipitate with deionized water and ethanol alternately, drying, introducing nitrogen in a tubular furnace at a flow rate of 100sccm, and pyrolyzing at a constant temperature of 900 ℃ for 2h at a heating rate of 3 ℃/min to obtain a tin/hard carbon compound;
(3) ball-milling the tin/hard carbon composite to reduce the particle size, wherein the ball-milling speed is 500rpm, the time is 0.5h, stirring and washing the tin/hard carbon composite for 8h by using 1mol/L excess dilute HCl solution, alternately centrifuging the mixture by using deionized water and ethanol to be neutral, and then drying the mixture in a 65 ℃ oven for 8h to obtain the nano tin/hard carbon composite electrode material for the sodium ion battery, wherein the carbon content of the nano tin/hard carbon composite electrode material is 62.8 wt%.
Fig. 1 is an X-ray diffraction pattern of the nano tin/hard carbon composite electrode material for the sodium ion battery obtained in example 1, wherein the ordinate is X-ray intensity, and the abscissa is X-ray scanning angle, as can be seen from fig. 1, the negative electrode material has characteristic peaks of obvious tin at scanning angles of 30.6 °, 32.1 °, 43.9 °, 44.9 °, 64.6 °, 72.4 ° and 79.5 °, which respectively correspond to crystal planes (200), (101), (220), (211), (321), (420) and (312) of Sn, and is tetragonal crystal Sn, and the X-ray diffraction pattern is consistent with standard card PDF # 04-0673. Weak tin oxide characteristic peaks appear at scanning angles of 26.6 ° and 33.9 °, corresponding to tin oxide crystal planes (200) and (101), respectively, indicating that the metallic Sn surface is oxidized.
Fig. 2 is a scanning electron microscope image of the nano tin/hard carbon composite electrode material for the sodium ion battery obtained in example 1, the size of the tin/hard carbon composite is 2-5 μm, no Sn aggregate is observed, which indicates that nano tin particles are not agglomerated but uniformly dispersed on lignin-derived hard carbon, and the size of the nano tin particles is 50-500 nm.
Example 2
The embodiment comprises the following specific steps:
(1) weighing 1g of enzymolysis lignin, 0.3g of stannous chloride dihydrate (SnCl)2 2H2O), 0.3g of polyvinylpyrrolidone is added into 50ml of distilled water and stirred uniformly, and then the dispersion is transferred to a hydrothermal kettle to react for 24 hours at 180 ℃ to obtain tin oxide/hydrothermal carbon composite precipitate;
(2) washing the precipitate with deionized water and ethanol alternately, drying, introducing nitrogen in a tubular furnace at the flow rate of 100sccm, and pyrolyzing at the constant temperature of 900 ℃ for 4h at the heating rate of 3 ℃/min to obtain a tin/hard carbon compound;
(3) ball-milling the tin/hard carbon composite to reduce the particle size, wherein the ball-milling speed is 500rpm, the time is 0.5h, stirring and washing the tin/hard carbon composite for 8h by using 1mol/L excess dilute HCl solution, alternately centrifuging the mixture by using deionized water and ethanol to be neutral, and then drying the mixture in a 65 ℃ oven for 8h to obtain the nano tin/hard carbon composite electrode material for the sodium ion battery, wherein the carbon content of the nano tin/hard carbon composite electrode material is 79.5 wt%.
Fig. 3 is an X-ray diffraction pattern of the nano tin/hard carbon composite electrode material for the sodium ion battery obtained in example 2, wherein the ordinate is X-ray intensity, and the abscissa is X-ray scanning angle, and it can be seen from fig. 3 that the anode material has distinct tin characteristic peaks at scanning angles of 30.6 °, 32.1 °, 43.9 °, 44.9 °, 64.6 °, 72.4 ° and 79.5 °, which respectively correspond to crystal planes (200), (101), (220), (211), (321), (420) and (312) of Sn, and is tetragonal crystal Sn, and the X-ray diffraction pattern is consistent with standard card PDF # 04-0673. Weak tin oxide characteristic peaks appear at scanning angles of 26.6 ° and 33.9 °, corresponding to tin oxide crystal planes (200) and (101), respectively, indicating that the metallic Sn surface is oxidized.
Fig. 4 is a scanning electron microscope image of the nano tin/hard carbon composite electrode material for the sodium ion battery obtained in example 2, the size of the tin/hard carbon composite is 2-5 μm, no Sn aggregate is observed, which indicates that nano tin particles are not agglomerated but uniformly dispersed on lignin-derived hard carbon, and the size of the nano tin particles is 50-500 nm.
Example 3
The embodiment comprises the following specific steps:
(1) weighing 1g of organic solvent lignin and 0.6g of stannous chloride dihydrate (SnCl)2 2H2O), 0.6g of polyvinylpyrrolidone is added into 50ml of distilled water and stirred uniformly, and then the dispersion is transferred to a hydrothermal kettle to react for 24 hours at 180 ℃ to obtain tin oxide/hydrothermal carbon composite precipitate;
(2) washing the precipitate with deionized water and ethanol alternately, drying, introducing nitrogen in a tubular furnace at the flow rate of 100sccm, and pyrolyzing at the constant temperature of 900 ℃ for 6h at the heating rate of 3 ℃/min to obtain a tin/hard carbon compound;
(3) ball-milling the tin/hard carbon composite to reduce the particle size, wherein the ball-milling speed is 500rpm, the time is 0.5h, stirring and washing the tin/hard carbon composite for 8h by using 1mol/L excess dilute HCl solution, alternately centrifuging the mixture by using deionized water and ethanol to be neutral, and then drying the mixture in a 65 ℃ oven for 8h to obtain the nano tin/hard carbon composite electrode material for the sodium ion battery, wherein the carbon content of the nano tin/hard carbon composite electrode material is 86.8 wt%.
Fig. 5 is an X-ray diffraction pattern of the nano tin/hard carbon composite electrode material for the sodium ion battery obtained in example 3, wherein the ordinate is X-ray intensity, and the abscissa is X-ray scanning angle, and as can be seen from fig. 5, the negative electrode material has characteristic peaks of obvious tin at scanning angles of 30.6 °, 32.1 °, 43.9 °, 44.9 °, 64.6 °, 72.4 ° and 79.5 °, which respectively correspond to Sn crystal planes (200), (101), (220), (211), (321), (420) and (312), and is tetragonal crystal Sn, and the X-ray diffraction pattern is consistent with standard card PDF # 04-0673. Weak tin oxide characteristic peaks appear at scanning angles of 26.6 ° and 33.9 °, corresponding to tin oxide crystal planes (200) and (101), respectively, indicating that the metallic Sn surface is oxidized.
Fig. 6 is a scanning electron microscope image of the nano tin/hard carbon composite electrode material for the sodium ion battery obtained in example 3, the size of the tin/hard carbon composite is 2-5 μm, no tin aggregate is observed, which indicates that nano tin particles are not aggregated but uniformly dispersed on lignin-derived hard carbon, and the size of the nano tin particles is 50-500 nm.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
Respectively taking the nano tin/hard carbon composite electrode material for the sodium ion battery prepared in each embodiment as a negative electrode active material, uniformly mixing the negative electrode active material, a binding agent polyvinylidene fluoride (PVDF) and a conductive agent (Super P) according to the mass ratio of 8: 1, uniformly coating a thin layer on an aluminum foil, drying the thin layer, cutting the thin layer into a wafer serving as the negative electrode material, taking a metal sodium sheet as a counter electrode, taking Whatman glass fiber as a diaphragm and taking 1.0mol/L NaClO4Ethylene Carbonate (EC) + Propylene Carbonate (PC) + Fluoroacetate (FEC) (EC to PC volume ratio 1: 1, FEC accounting for 5% of the total volume) as electrolyte were respectively assembled into CR2032 coin cells in an argon glove box.
The button cell is tested by a blue battery tester produced by Jinnuo electronics, Inc. in Wuhan, the test conditions and results are as follows:
the button cell is subjected to constant-current charge and discharge test, the charge and discharge voltage range is 0.01-2.5V, the initial discharge specific capacity is 104-231 mAh/g under the current density of 100mA/g, the discharge specific capacity is 94-223 mAh/g after 200 cycles of circulation, and the coulombic efficiency is close to 100%; under the condition of high current density of 1A/g, the initial discharge specific capacity is 30-131 mAh/g, the discharge specific capacity after 1000 cycles is 28-120 mAh/g, and the discharge specific capacity of the battery is kept to be more than 92% of the initial discharge capacity.
According to the prepared nano tin/hard carbon composite electrode material for the sodium ion battery, Sn nano particles can be uniformly dispersed on a lignin-derived hard carbon carrier, and the volume expansion of Sn during charge-discharge circulation is effectively relieved. In example 2, under 100mA/g, the discharge specific capacity of the battery after 200 cycles is 223mAh/g, the capacity retention rate is 96.5%, and under the condition of high current density of 1A/g, the capacity retention rate reaches 92% after 1000 cycles, in examples 1 and 3, the distribution and the content of Sn are affected by too high or too low carbon content, and both the examples show lower specific capacity, and specific data are shown in Table 1.
TABLE 1 test results
Claims (10)
1. A preparation method of a nano tin/hard carbon composite electrode material for a sodium ion battery is characterized by comprising the following steps:
(1) dispersing or dissolving lignin, inorganic tin compound and surfactant in water, and stirring to obtain uniform dispersion liquid;
(2) placing the dispersion liquid obtained in the step (1) in a hydrothermal kettle to perform hydrothermal reaction under certain conditions to obtain a tin oxide/hydrothermal carbon composite precipitate;
(3) washing and drying the tin oxide/hydrothermal carbon composite precipitate obtained in the step (2), and pyrolyzing the tin oxide/hydrothermal carbon composite precipitate at high temperature in a tubular furnace under inert atmosphere to obtain a nano tin/hard carbon composite;
(4) and (4) carrying out ball milling, washing and drying on the nano tin/hard carbon composite obtained in the step (3) to obtain the nano tin/hard carbon composite electrode material for the sodium ion battery.
2. The method for preparing the nano tin/hard carbon composite electrode material for the sodium ion battery according to claim 1, wherein the lignin in the step (1) comprises one or more of enzymatic lignin, alkali lignin, organic solvent lignin, sulfonated lignin and lignosulfonate; the inorganic tin compound includes one or more of stannous chloride dihydrate, stannic chloride pentahydrate, stannous chloride anhydrate, and stannic chloride pentahydrate.
3. The method for preparing the nano tin/hard carbon composite electrode material for the sodium-ion battery as claimed in claim 1, wherein the surfactant in the step (1) comprises one or more of polyvinylpyrrolidone and ammonium dihydrogen phosphate, and the water is at least deionized water.
4. The preparation method of the nano tin/hard carbon composite electrode material for the sodium ion battery as claimed in claim 1, wherein the mass ratio of the lignin, the inorganic tin compound, the surfactant and the water in the step (1) is 1: 0.1-3: 10-80.
5. The preparation method of the nano tin/hard carbon composite electrode material for the sodium ion battery according to claim 1, wherein the hydrothermal carbonization temperature in the step (2) is 150-300 ℃, the reaction time is 1-48 h, and the filling degree of a hydrothermal kettle is 30% -90%.
6. The preparation method of the nano tin/hard carbon composite electrode material for the sodium ion battery according to claim 1, wherein the washing solvent in the step (3) is deionized water or absolute ethyl alcohol, the drying temperature is 60-150 ℃, and the drying time is 1-36 h.
7. The preparation method of the nano tin/hard carbon composite electrode material for the sodium ion battery according to claim 1, wherein the pyrolysis temperature in the step (3) is 600-1600 ℃, the pyrolysis time is 0.5-24 h, the temperature rise rate is 1-20 ℃/min, and the inert gas is N2One of Ar and He, and the flow rate of the inert gas is 5-200 sccm.
8. The preparation method of the nano tin/hard carbon composite electrode material for the sodium ion battery as claimed in claim 1, wherein in the step (4), the ball milling rotation speed is 100-1200 rpm, the ball milling time is 0.5-10 h, and the particle size after ball milling is 2-10 μm. In order to remove impurities, dilute hydrochloric acid or dilute sulfuric acid water solution is used for washing, the concentration is 0.1-1 mol/L, then deionized water and ethanol are used for alternately centrifuging to be neutral, and finally the nano tin/hard carbon composite material is obtained through drying, wherein the drying temperature is 60-150 ℃, and the drying time is 1-36 hours.
9. The nano tin/hard carbon composite electrode material for the sodium ion battery is characterized by being prepared by the preparation method of the nano tin/hard carbon composite electrode material for the sodium ion battery according to any one of claims 1 to 8, wherein the carbon content of the electrode material is 10-90 wt%.
10. A sodium ion battery with the electrode material of the nano tin/hard carbon composite electrode material for the sodium ion battery in claim 9.
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