CN114094062A - Preparation method and application of oxalic acid assisted synthesis of tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material - Google Patents
Preparation method and application of oxalic acid assisted synthesis of tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material Download PDFInfo
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- CN114094062A CN114094062A CN202111177997.4A CN202111177997A CN114094062A CN 114094062 A CN114094062 A CN 114094062A CN 202111177997 A CN202111177997 A CN 202111177997A CN 114094062 A CN114094062 A CN 114094062A
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- tin dioxide
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- oxalic acid
- graphene
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 221
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 172
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 57
- 238000003860 storage Methods 0.000 title claims abstract description 44
- 239000011734 sodium Substances 0.000 title claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 34
- 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 title claims abstract description 32
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011232 storage material Substances 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 239000007773 negative electrode material Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 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 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229960005261 aspartic acid Drugs 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 3
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 3
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 229940079864 sodium stannate Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 8
- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 abstract description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Substances O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 abstract description 6
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 abstract description 4
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- 239000012798 spherical particle Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
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- 229910020462 K2SnO3 Inorganic materials 0.000 description 1
- 229910002980 Li4.4Sn Inorganic materials 0.000 description 1
- 229910004751 Na15Sn4 Inorganic materials 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
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- 238000006138 lithiation reaction Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- -1 small molecule organic acid Chemical class 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method and application of a high-performance lithium storage and sodium storage material of stannic oxide nanoparticle composite graphene through oxalic acid assisted synthesis. The invention adopts a simple one-step solvothermal method to synthesize a spherical particle aggregate stannic oxide with the concentration of about 30 nanometers by using tin (II) chloride dihydrate, small molecular organic acid and oxalic acid as raw materials, and the material takes oxalic acid as a precipitateThe precipitating agent obtains SnO by utilizing the conversion process from the tin oxalate micron rod to the tin dioxide nano particles2Nanoparticles, which are spherical nanoparticles. Then SnO2The nano particles are compounded with the conductive graphene, and the nano tin dioxide particles are uniformly wrapped in the graphene oxide, so that the pulverization and the falling of the material caused by the volume expansion of the material in the circulation process are relieved, the conductivity of the material is improved, and the high capacity and the high circulation stability of the high-performance lithium and sodium storage material compounded by the tin dioxide nano particles and the graphene are realized.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method and application of a high-performance lithium storage and sodium storage material of stannic oxide nanoparticle composite graphene through oxalic acid assisted synthesis.
Background
Lithium Ion Batteries (LIBs) have many advantages such as high energy density, long cycle life, and environmental friendliness, and play a leading role in a wide range of applications. However, the theoretical capacity of LIB commercial graphite anodes is only 372 mAh g-1In order to further significantly improve the energy density of LIB, a new high-performance lithium-storage negative electrode material is actively explored. Furthermore, scarcity of lithium resources in the crust leads to high cost of LIBs, which limits their widespread use in smart grids and large-scale energy storage systems. Thus, Sodium Ion Batteries (SIBs) have been widely studied due to their similar operating principle to LIBs, while sodium has abundant resources and a lower price. However, the radius of sodium ions is larger than that of lithium ions, so that commercialized LIB cathode graphite cannot be directly used in SIB, and there is no currently recognized SIB cathode material that can be produced and commercialized, and therefore, it is urgent to develop an inexpensive and commercialized SIB cathode material.
Tin dioxide (SnO)2) Due to relatively high theoretical lithium and sodium storage reversible capacity (lithium storage capacity 1494 mAh g)-11378 mAh g of sodium storage capacity-1) Low cost, high abundance, easy synthesis, high safety and the like, and is widely concerned. Tin dioxide is known as a LIBs anode material with a moderate lithiation potential (≈ 1.0V vs Li/Li)+) And storing Li by two reaction processes+I.e. the first conversion reaction (SnO)2 + 4Li++4e-↔Sn + 2Li2O) productionRaw 711 mAh g-1Capacity of (b), second alloying reaction (Sn + 4.4 Li)++4.4e-↔Li4.4Sn) contributes 783 mAh g-1The capacity of (c). Tin dioxide as a material for SIBs negative electrodes, storing Na by two reaction processes+I.e. the first conversion reaction (SnO)2 +4Na+ + 4e- ↔Sn + 2Na2O) produced 711 mAh g-1Capacity of (b), second alloying reaction (Sn + 3.75 Na)++ 3.75e- ↔Na3.75Sn（Na15Sn4) 667 mAh g are contributed-1The capacity of (c). However, realization of SnO2The high sodium storage capacity of lithium is hampered by two major problems. The first is SnO in the process of lithium sodium intercalation and deintercalation2The bulk of the particles changes, causing pulverization of the electrode and loss of electrical contact, resulting in a rapid drop in capacity. The second key problem is that the metal Sn particles are coarsened continuously in the circulating process, so that the reversibility of the electrochemical reaction is attenuated continuously, and the capacity is reduced gradually. These factors all severely limit SnO2The application in LIBs and SIBs.
One effective improvement strategy is to anchor the nano-sized tin dioxide particles in a conductive carbon matrix. The reduction of the size of the tin dioxide can realize high reaction activity and capacity improvement, and the anchoring in the conductive carbon material matrix can improve the conductivity and inhibit the coarsening of the metal tin particles to improve the cycle stability. Graphene is considered to be one of the most effective conductive carbon matrices because it has a unique two-dimensional structure, a high specific surface area, excellent conductivity, and a unique surface electronic structure.
Therefore, in order to further improve the electrochemical performance of the tin dioxide lithium-storage sodium-storage negative electrode, the exploration and preparation of nano-scale tin dioxide are particularly critical.
The Chinese invention patent with the patent number of 201910784530.2 discloses that tin dioxide/metal simple substance/graphene ternary composite material is obtained by taking tin salt and metal salt as raw materials through a one-pot method in an electrostatic adsorption mode and is used as a lithium battery negative electrode material, and after 200 cycles under the current density of 0.1A/g, the specific capacity is 891 mAh g-1；
The Chinese invention patent with the patent number of 201410737538.0 discloses that hollow tin dioxide and graphene oxide prepared by hydrothermal method are used as raw materials, the hollow tin dioxide composite material rolled by graphene is obtained by cold quenching, freeze drying and reduction under the condition of inert atmosphere and is used as a negative electrode material of a lithium battery, the specific discharge capacity after 50 cycles is 1156 mAh/g at the charging and discharging rate of 100 mA/g, and the specific discharge capacities at the charging and discharging rates of 200 mA/g, 500 mA/g, 1A/g, 2A/g and 5A/g are respectively: 954. 762, 610, 490 and 395 mAh/g.
The Chinese invention patent with the patent number of 202110542148.8 discloses that a carbon-coated tin dioxide material is synthesized by a hydrothermal method by taking tin salt, urea and an organic carbon source as raw materials to serve as a sodium-electricity negative electrode material, and the first charge-discharge specific capacity is 603 mAh/g under the current density of 0.1A/g. Linlin Fan et al synthesized amorphous SnO from tin (II) chloride dihydrate, graphene oxide and ethylene glycol by hydrothermal method2Graphene aerogel (a-SnO)2/GA) nanocomposite material as sodium electric anode material, at 50 mA g-1The capacity after 100 cycles at the current density of (A) was 380.2 mAh g-1（Adv. Energy Mater. 2016, 6, 1502057）；
Fanghua Tian et al prepared SnO from polyvinylpyrrolidone, tin (II) chloride dihydrate and N, N-dimethylformamide as raw materials by electrostatic spinning method2When the @ Carbon nanowire is used as a negative electrode material of the lithium battery, the g is 100 mA-1The capacity after 50 cycles under the current density is 680 mAh g-1（Materials Letters 284 (2021) 129019）；
Quang Nhat Tran et al prepared SnO from nanocrystalline cellulose (CNC), tin (II) chloride dihydrate and sodium citrate dihydrate by hydrothermal method and annealing technology2The nano flower is used as an active LIB cathode material and is added at 100 mA g-1Current density of 891 mAh g as initial reversible capacity-1（Materials 2020, 13, 3165）；
Xianfeng Du et al uses methyl orange, iron (III) chloride hexahydrate, pyrrole, ethylene glycol, tin (II) chloride dihydrate, polyvinylidene fluoride and N-methyl-2-pyrrolidone as raw materials and is prepared by passing mesoporous SnO2AnchoringFabrication of nanostructured SnO on robust polypyrrole nanotubes2The composite material is used as an LIB anode material and is used at 2000 mA g-1Has a current density of about 770 mAh g-1Specific capacity of 200 mA g-1Under the current density, the capacity after charging and discharging for 200 circles is about 790 mAh g-1（ACS Appl. Mater. Interfaces 2016, 8, 15598−15606）；
Xixin Chen expressed as K2SnO3·3H2SnO is prepared by taking O, urea, ethanol and deionized water as raw materials2Nanospheres of Graphene Oxide (GO), vitamin C and SnO2Reduced graphene oxide and SnO are prepared in solution2The nanosphere composite material is used as an LIB negative electrode material and is added at 1000 mA g-1The capacity after 100 cycles under the current density is 400 mAh g-1As the SIB negative electrode material, at 100 mA g-1The capacity after 100 cycles under the current density is 212 mAh g-1（ChemistrySelect 2021, 6, 3192–3198）；
The tin dioxide particles synthesized by the conventional method have complex operation and unsatisfactory performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method and application of a high-performance lithium-storing and sodium-storing material for synthesizing tin dioxide nanoparticle composite graphene under the assistance of oxalic acid.
The technical scheme adopted by the invention is as follows: a preparation method of a high-performance lithium-storing and sodium-storing material for synthesizing stannic oxide nanoparticle composite graphene under the assistance of oxalic acid comprises the following steps:
s1: adding soluble tin salt and micromolecular organic acid into ultrapure water, uniformly mixing, adding an organic solvent, and uniformly stirring to obtain a solution A; adding oxalic acid into ultrapure water to obtain a solution B;
s2: dropwise adding the solution B into the solution A, and stirring to uniformly mix the solution B and the solution A to obtain a solution C;
s3: placing the solution C in a closed space, heating to 60-200 ℃ for reaction, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain tin dioxide nanoparticles;
s4: dispersing tin dioxide nanoparticles and graphene oxide in water, performing ball milling, and removing liquid to obtain a tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material;
the organic solvent is ethanol, glycol or glycerol.
The soluble stanniferous compound is sodium stannate, potassium stannate, stannic sulfate, stannous chloride, stannous acetate or stannic chloride.
The small molecular organic acid is salicylic acid, DL-malic acid, ascorbic acid, malonic acid, citric acid or L-aspartic acid.
The graphene is prepared by an optimized Hummers method.
The ratio of the tin dioxide nanoparticles to the graphene oxide is 4-8: 1.
The tin dioxide nanoparticle composite graphene high-performance lithium-storage and sodium-storage material prepared by the preparation method for synthesizing the tin dioxide nanoparticle composite graphene high-performance lithium-storage and sodium-storage material with the assistance of oxalic acid.
The cathode material contains the tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material.
The preparation method comprises the following steps: weighing oxalic acid for assisting in synthesizing the tin dioxide nanoparticle composite graphene high-performance lithium storage sodium material, acetylene black and sodium alginate, uniformly mixing, adding a solvent, stirring into paste, and coating on a current collector.
The lithium ion battery containing the anode material is provided.
A sodium ion battery containing the negative electrode material as described above.
The invention has the following beneficial effects: according to the preparation method, a dissolving heat reaction that tin oxalate is converted into tin dioxide nano-particles is initiated by a precipitator oxalic acid is utilized, the appearance of tin dioxide is regulated and controlled by a small molecular organic acid, then the tin dioxide nano-particles and graphene are uniformly compounded through ball milling, and the prepared tin dioxide nano-particle composite graphene shows excellent lithium storage and sodium storage performances. The appearance of tin dioxide can be regulated and controlled to a certain extent by the added micromolecular organic acid, organic solvent and precipitator, the existence of oxalic acid enables the unique tin oxalate micron rod generated in the solvothermal reaction to be converted into tin dioxide nano particles, and the micromolecular organic acid can be adsorbed on the surfaces of the tin dioxide nano particles to play a stabilizing role and can stabilize small crystal regions. Then, the synthesized tin dioxide nano particles and the graphene conductive matrix are uniformly compounded, so that the conductivity is improved, the volume expansion effect is relieved, and the coarsening of tin particles is inhibited, therefore, the composite material is used as a negative electrode material of a lithium ion battery and a sodium ion battery, has high specific capacity and long cycle life, and realizes high lithium storage and sodium storage performances.
In some embodiments of the invention, the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material is prepared into an LIB cathode at 100 mA g-1The capacity of the current after 50 times of circulation is up to 1378 mAh g-1At 1000 mA g-1The capacity of the alloy reaches 1739 mAh g after 500 cycles of current-1(ii) a Preparing a tin dioxide nanoparticle composite graphene high-performance lithium-storage sodium-storage material into an SIB negative electrode SnO2the/GO nano composite material is at 50 mA g-1The capacity of the current is up to 485 mAh g after 60 times of circulation-1At 200 mA g-1The capacity is kept to 337 mAh g after 100 times of circulation under the current-1. The performance is significantly higher than the results reported in the prior art patents and published articles.
The invention adopts a simple one-step solvothermal method to synthesize a spherical particle aggregate stannic oxide with the concentration of about 30 nanometers by using tin (II) chloride dihydrate, small molecular organic acid and oxalic acid as raw materials, and the material takes oxalic acid as a precipitator and utilizes the conversion process of tin oxalate micro-rods to stannic oxide nano-particles to obtain SnO2Nanoparticles, which are spherical nanoparticles. Then SnO2The nano particles are compounded with the conductive graphene, and the nano tin dioxide particles are uniformly wrapped in the graphene oxide, so that the pulverization and the falling of the material caused by the volume expansion of the material in the circulation process are relieved, the conductivity of the material is improved, and the high capacity and the high circulation stability of the high-performance lithium and sodium storage material compounded by the tin dioxide nano particles and the graphene are realized. The invention firstly proposes that the stannic oxalate is slightlyThe rice rods are converted into the tin dioxide nano particles, so that higher capacity and better cycle stability are provided for the lithium ion battery and the sodium ion battery.
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 introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a Scanning Electron Microscope (SEM) picture (a, c), a Transmission Electron Microscope (TEM) picture (b, d) and an X-ray diffraction pattern (XRD) (e) of the tin dioxide particles prepared in example 1;
fig. 2 is Scanning Electron Microscope (SEM) images (a, b) and Transmission Electron Microscope (TEM) images (c, d) of the tin dioxide particle composite graphene prepared in example 1;
FIG. 3 is a cycling stability test chart (a, b, e) of the tin dioxide particle composite graphene lithium storage negative electrode material prepared in example 1 at current densities of 100 mA g-1 and 1000 mA g-1 and different multiplying powers and a charge-discharge curve test chart (c, d) at current density of 1000 mA g-1;
FIG. 4 is a cycling stability test chart (a, b) of the tin dioxide particle composite graphene sodium storage negative electrode material prepared in example 1 at current densities of 50 mA g-1 and 200 mA g-1 and a charge-discharge curve test chart (c, d) at current density of 50 mA g-1;
FIG. 5 shows that the amount of oxalic acid added in example 2 is increased to synthesize tin dioxide nanoparticle composite graphene used as the negative electrode of the lithium ion battery at 1000 mA g-1Graph of cycling stability at current density.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
It should be noted that all expressions using "first" and "second" in the embodiments of the present invention are used for distinguishing two entities with the same name but different names or different parameters, and it should be noted that "first" and "second" are merely for convenience of description and should not be construed as limitations of the embodiments of the present invention, which are not described in any more detail in the following embodiments.
The terms of direction and position of the present invention, such as "up", "down", "front", "back", "left", "right", "inside", "outside", "top", "bottom", "side", etc., refer to the direction and position of the attached drawings. Accordingly, the use of directional and positional terms is intended to illustrate and understand the present invention and is not intended to limit the scope of the present invention.
The invention provides a preparation method of a high-performance lithium-storing and sodium-storing material for synthesizing stannic oxide nano-particle composite graphene under the assistance of oxalic acid, which comprises the following steps:
s1: adding soluble tin salt and micromolecular organic acid into ultrapure water, uniformly mixing, adding an organic solvent, and uniformly stirring to obtain a solution A; adding oxalic acid into ultrapure water to obtain a solution B;
s2: dropwise adding the solution B into the solution A, and stirring to uniformly mix the solution B and the solution A to obtain a solution C;
s3: placing the solution C in a closed space, heating to 60-200 ℃ for reaction, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain tin dioxide nanoparticles;
s4: dispersing tin dioxide nanoparticles and graphene oxide in water, performing ball milling, and removing liquid to obtain a tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material;
the organic solvent is ethanol, glycol or glycerol.
In some embodiments of the invention, the soluble tin-containing compound is sodium stannate, potassium stannate, stannic sulfate, stannous chloride, stannous acetate, or stannic chloride.
In some embodiments of the invention, the small molecule organic acid is salicylic acid, DL-malic acid, ascorbic acid, malonic acid, citric acid, or L-aspartic acid.
In some embodiments of the invention, the solution C is sealed in a reaction kettle, and placed in an oven at 60-200 ℃ for reaction, preferably, the reaction temperature is preferably 100-190 ℃. In some embodiments of the invention, the reaction time is specifically 15-20 h. In some embodiments of the present invention, the product of step S3 is washed with water and ethanol 3 times, and then dried in an oven at 80 ℃.
In some embodiments of the invention, the product tin dioxide nanoparticles are dispersed with graphene oxide in water, transferred to a 50 ml zirconia milling jar, charged with 300 zirconia milling balls of 5mm diameter and ball milled for 6 hours at 1200 rpm with a swing ball mill motor.
In some embodiments of the invention, the graphene is prepared by an optimized Hummers method.
In some embodiments of the invention, the ratio of the tin dioxide nanoparticles to graphene oxide is 4-8: 1.
The tin dioxide nanoparticle composite graphene high-performance lithium-storage and sodium-storage material prepared by the preparation method for synthesizing the tin dioxide nanoparticle composite graphene high-performance lithium-storage and sodium-storage material with the assistance of oxalic acid.
The cathode material contains the tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material.
In some embodiments of the present invention, the method of making comprises the steps of: weighing oxalic acid for assisting in synthesizing the tin dioxide nanoparticle composite graphene high-performance lithium storage sodium material, acetylene black and sodium alginate, uniformly mixing, adding a solvent, stirring into paste, and coating on a current collector.
The lithium ion battery containing the anode material is provided.
A sodium ion battery containing the negative electrode material as described above.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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.
Example 1
A preparation method of a high-performance lithium-storing and sodium-storing stannic oxide nanoparticle composite graphene material assisted by oxalic acid comprises the following steps:
s1: weighing 1mmoLSnCl in a reaction kettle2·2H2Adding 5mL of ultrapure water into O and 1mmol of tartaric acid, carrying out ultrasonic mixing uniformly, adding 25mL of ethylene glycol, transferring to a magnetic stirrer at a certain temperature, and stirring for a period of time to obtain a solution A. 3mmol oxalic acid is weighed and added into 10mL ultrapure water in a beaker, and the solution B is obtained after the ultrasonic mixing is uniform.
S2: dropwise adding the solution B into the solution A, and magnetically stirring for 10 minutes to uniformly mix the solution B and the solution A to obtain a solution C. And sealing the solution C in the reaction kettle, putting the solution C into a 180 ℃ oven, and reacting for 20 hours. After the reaction is finished, the reaction kettle is quickly cooled to room temperature. Centrifuging all the solutions, sequentially cleaning the products for 3 times by water and ethanol, and drying in an oven at 80 ℃ for 8 hours to obtain a powdery product, namely the tin dioxide nanoparticles.
S3: mixing the product tin dioxide nanoparticles with graphene oxide in a ratio of 4: the ratio of 1 is dispersed in 30 ml of water, the mixture is transferred to a 50 ml zirconia ball milling tank, 300 zirconia grinding balls with the diameter of 5mm are added, the mixture is ball milled for 6 hours under the condition that the motor of the oscillating ball mill rotates at the speed of 1200 r/min, and then the dispersion liquid is stirred and evaporated in an oil bath at the temperature of 80 ℃ to obtain the oxalic acid-assisted synthesis tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material.
In order to prove the high lithium storage and sodium storage performance of the oxalic acid-assisted synthesis of the tin dioxide nanoparticle composite graphite, in step S1 of embodiment 1, 3mmol of oxalic acid is not added, and the oxalic acid-assisted-free tin dioxide particle composite graphene is synthesized by comparison.
Example 2
A preparation method of a high-performance lithium-storing and sodium-storing stannic oxide nanoparticle composite graphene material assisted by oxalic acid comprises the following steps:
s1: weighing 1mmoLSnCl in a reaction kettle2·2H2Adding 5mL of ultrapure water into O and 1mmol of ascorbic acid, uniformly mixing by ultrasonic, adding 25mL of glycerol, transferring to a magnetic stirrer at a certain temperature, and stirring for a period of time to obtain a solution A. 5mmol oxalic acid is weighed and added into 10mL ultrapure water in a beaker, and the solution B is obtained after the ultrasonic mixing is uniform.
S2: dropwise adding the solution B into the solution A, and magnetically stirring for 10 minutes to uniformly mix the solution B and the solution A to obtain a solution C. And sealing the solution C in the reaction kettle, putting the solution C into a 160 ℃ oven, and reacting for 15 h. After the reaction is finished, the reaction kettle is quickly cooled to room temperature. Centrifuging all the solutions, sequentially cleaning the products for 3 times by water and ethanol, and drying in an oven at 80 ℃ for 8 hours to obtain a powdery product, namely the tin dioxide nanoparticles.
S3: mixing the product tin dioxide nano-particles with graphene oxide in a ratio of 8: the ratio of 1 is dispersed in 30 ml of water, the mixture is transferred to a 50 ml zirconia ball milling tank, 300 zirconia grinding balls with the diameter of 5mm are added, the mixture is ball milled for 6 hours under the condition that the motor of the oscillating ball mill rotates at the speed of 1200 r/min, and then the dispersion liquid is stirred and evaporated in an oil bath at the temperature of 80 ℃ to obtain the oxalic acid-assisted synthesis tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material.
Microscopic characterization
The following are microscopic representations of different means for oxalic acid-assisted synthesis of a tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material:
FIG. 1 is SEM image (a) and TEM image (b) of oxalic acid-assisted synthesized tin dioxide nanoparticles in example 1; SEM image (c) and TEM image (d) of tin dioxide particles synthesized without oxalic acid addition; the X-ray diffraction patterns (XRD) of the oxalic acid-assisted synthesized tin dioxide nanoparticles were compared to those of tin dioxide particles synthesized without oxalic acid. The comparison between SEM and TEM shows that the size of the tin dioxide nanoparticles synthesized by oxalic acid in the example 1 is about 20-30 nm, the morphology is an aggregate of spherical particles, and the size is uniform; the tin dioxide prepared without oxalic acid has larger particle size, various shapes and nonuniform size. It can be seen by XRD that both materials synthesized in embodiment 1 are tin dioxide.
Fig. 2 is SEM (a) and TEM (b) of oxalic acid assisted synthesis of tin dioxide nanoparticle composite graphene in example 1; and (d) comparing an SEM image (c) and a TEM image (d) of the tin dioxide particle composite graphene synthesized without oxalic acid, wherein the effect of the tin dioxide nanoparticle composite graphene synthesized with the assistance of oxalic acid is better, and the tin dioxide nanoparticles are uniformly dispersed in the graphene.
The morphology of the product of example 2 is relatively similar to that of example 1.
Characterization of electrochemical Properties
FIG. 3 shows that the oxalic acid assisted synthesis of tin dioxide nanoparticle composite graphene and the oxalic acid-free synthesis of tin dioxide nanoparticle composite graphene in example 1 are used as the negative electrode of a lithium ion battery at 100 mA g-1Graph (a), 1000 mA g-1Graph (b) and different multiplying power graph (e) the current density under the test chart of the circulation stability and the current density at 1000 mA g-1Graphs (c, d) are charge/discharge curve test charts at current density. As can be seen from comparison of the cycle stability performance graphs, the oxalic acid assisted synthesis of the tin dioxide nanoparticle composite graphene lithium storage negative electrode material in the example 1 is 100 mA g-1The capacity of 1378 mAh g is still left after the current is circulated to 50 circles under the current density-1(ii) a At 1000 mA g-1Under the current density, the capacity is increased to 1739 mAh g after the current is circulated to 500 circles-1(ii) a At different multiplying power, at 2000 mA g-1The capacity under the current condition is as high as 1037 mAh g-1. Example 1 preparation of tin dioxide nanoparticle composite graphene lithium storage negative electrode material without oxalic acid at 100 mA g-1The capacity is 533 mA g after the current is circulated to 50 circles under the current density-1(ii) a At 1000 mA g-1Under the current density, the capacity is 365 mAh g after the circulation is carried out for 500 circles-1(ii) a At different multiplying power, at 2000 mA g-1Capacity under current condition is only 500 mAh g-1. The oxalic acid assisted synthesis of the tin dioxide nanoparticle composite graphene high-performance lithium storage sodium material is proved to have good cycling stability and high capacity when used as the lithium ion battery cathode.
FIG. 4 shows the synthesis of oxalic acid-assisted tin dioxide nanoparticle composite graphene and the synthesis of graphene without oxalic acid in example 1The cathode of the sodium ion battery using the tin oxide particle composite graphene is 50 mA g-1Graphs (a) and 200 mA g-1Graph (b) Cyclic stability test at Current Density and at 50 mA g-1Graphs (c, d) are charge/discharge curve test charts at current density. As can be seen from comparison of the cycle stability performance graphs, the oxalic acid assisted synthesis of the tin dioxide nanoparticle composite graphene sodium storage negative electrode material in example 1 is 50 mA g-1The first discharge capacity was 1151.8 mAh g at current density-1The capacity is 485 mAh g after circulating to 60 circles-1(ii) a At 200 mA g-1The first discharge capacity was 1216.2 mAh g at current density-1After circulating to 100 circles, the capacity is 337 mAh g-1. Example 1 preparation of tin dioxide nanoparticle composite graphene sodium storage negative electrode material without oxalic acid at 50 mA g-1The first discharge capacity was 571.5 mAh g at current density-1The capacity after circulating to 60 circles is 293 mA g-1(ii) a At 200 mA g-1The first discharge capacity was 646.7 mAh g at current density-1The capacity is 254 mA g after circulating to 100 circles-1. The oxalic acid assisted synthesis of the tin dioxide nanoparticle composite graphene high-performance lithium storage sodium material is shown to be used as the sodium ion battery cathode, and the cycle stability and the capacity are also good.
FIG. 5 shows that the amount of oxalic acid added in example 2 is increased to synthesize tin dioxide nanoparticle composite graphene used as the negative electrode of the lithium ion battery at 1000 mA g-1Graph of cycling stability at current density. As can be seen from the graph, the capacity increased to 1307 mAh g after the circulation of 500 cycles-1. The invention can prepare the tin dioxide nano-particles with good performance through fine adjustment experiments.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. A preparation method of a high-performance lithium-storing and sodium-storing material for synthesizing stannic oxide nano-particle composite graphene under the assistance of oxalic acid is characterized by comprising the following steps:
s1: adding soluble tin salt and micromolecular organic acid into ultrapure water, uniformly mixing, adding an organic solvent, and uniformly stirring to obtain a solution A; adding oxalic acid into ultrapure water to obtain a solution B;
s2: dropwise adding the solution B into the solution A, and stirring to uniformly mix the solution B and the solution A to obtain a solution C;
s3: placing the solution C in a closed space, heating to 60-200 ℃ for reaction, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain tin dioxide nanoparticles;
s4: dispersing tin dioxide nanoparticles and graphene oxide in water, performing ball milling, and removing liquid to obtain a tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material;
the organic solvent is ethanol, glycol or glycerol.
2. The preparation method of the high-performance lithium-storing and sodium-storing material of the tin dioxide nanoparticle composite graphene, which is synthesized by the assistance of oxalic acid, according to claim 1, is characterized in that: the soluble stanniferous compound is sodium stannate, potassium stannate, stannic sulfate, stannous chloride, stannous acetate or stannic chloride.
3. The preparation method of the high-performance lithium-storing and sodium-storing material of the tin dioxide nanoparticle composite graphene, which is synthesized by the assistance of oxalic acid, according to claim 1, is characterized in that: the small molecular organic acid is salicylic acid, DL-malic acid, ascorbic acid, malonic acid, citric acid or L-aspartic acid.
4. The preparation method of the high-performance lithium-storing and sodium-storing material of the tin dioxide nanoparticle composite graphene, which is synthesized by the assistance of oxalic acid, according to claim 1, is characterized in that: the graphene is prepared by an optimized Hummers method.
5. The preparation method of the high-performance lithium-storing and sodium-storing material of the tin dioxide nanoparticle composite graphene, which is synthesized by the assistance of oxalic acid, according to claim 1, is characterized in that: the ratio of the tin dioxide nanoparticles to the graphene oxide is 4-8: 1.
6. The tin dioxide nanoparticle composite graphene high-performance lithium-storage and sodium-storage material prepared by the preparation method for the oxalic acid-assisted synthesis of the tin dioxide nanoparticle composite graphene high-performance lithium-storage and sodium-storage material according to any one of claims 1 to 5.
7. A negative electrode material containing the tin dioxide nanoparticle composite graphene high-performance lithium storage and sodium storage material as claimed in claim 6.
8. The negative electrode material according to claim 7, characterized in that the preparation method thereof comprises the steps of: weighing oxalic acid for assisting in synthesizing the tin dioxide nanoparticle composite graphene high-performance lithium storage sodium material, acetylene black and sodium alginate, uniformly mixing, adding a solvent, stirring into paste, and coating on a current collector.
9. A lithium ion battery comprising the negative electrode material of claim 7.
10. A sodium ion battery comprising the anode material of claim 7.
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