CN102208638B - High-capacity lithium ion battery cathode composite material and preparation method thereof - Google Patents
High-capacity lithium ion battery cathode composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 150000003606 tin compounds Chemical class 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000014121 butter Nutrition 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 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 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 8
- 230000004087 circulation Effects 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 4
- 229910006854 SnOx Inorganic materials 0.000 abstract 4
- 239000000758 substrate Substances 0.000 abstract 1
- 239000011135 tin Substances 0.000 description 33
- 229910006404 SnO 2 Inorganic materials 0.000 description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of preparation and application of energy materials, and relates to a novel lithium ion battery cathode material and a preparation method thereof. The components of the high-capacity lithium ion battery cathode composite material are composite powder materials of SnOx/C or SnOx/Sn/C, wherein x is greater than 1 and less than or equal to 2, carbon content is 20-80percent by weight, the particle size of the composite materials is 0.5-50 microns, SnOx and Sn in the composite material have the particle size in nanometers or submicrons, and the SnOx and the Sn are dispersed and distributed in a carbon substrate. The first reversible capacity of the composite material as the cathode material of the lithium ion battery is 430-650 mAh/g, after circulation for initial several times or more than ten times, the materials display good circulation stability. The composite materials have a particular amount of SnO2 or also have a certain amount of Sn, and the densities of SnO2 and Sn are respectively up to 6.0 g/cm<3> and 7.3 g/cm<3>, which is double or triple of carbon density, thus, the volume capacity of the battery can be greatly improved by using the composite materials as the cathode materials of the lithium ion battery.
Description
Technical field
The invention belongs to preparation and the application of energy and material, relate to Novel cathode material for lithium ion battery and preparation method thereof.
Technical background
As a kind of eco-friendly high-energy density secondary power supply, lithium ion battery is used widely in the small portable apparatus such as notebook computer, mobile phone.Than lead-acid battery, nickel-cadmium cell, Ni-MH battery, lithium ion battery has the energy density height, has extended cycle life, self discharge is little, memory-less effect, to the advantage such as the pollution of environment is little.Fast development along with modern society, energy shortage and problem of environmental pollution day are aobvious serious, and lithium ion battery needs the user demand of high power density and high-energy-density power supply day by day urgent at electric automobile, hybrid vehicle, electric bicycle, solar energy and wind energy storage and conversion, movable electric tool, mid power household electrical appliance etc.The positive and negative electrode material plays a key effect to the performance of lithium ion battery, and present commercial Li-ion batteries is because its positive electrode LiCoO
2With the capacity limitation (its theoretical capacity is about respectively 140mAh/g and 372mAh/g) of negative material graphitic carbon, the requirement of the above-mentioned high power density of distance and high-energy-density power supply also has larger distance.As the graphitic carbon of negative material, its density only has 2.2～2.4g/cm
3, this has reduced the volume capacity of battery to a great extent, and is particularly unfavorable to large-scale high power density battery.And for LiCoO
2Positive electrode, except the limitation of its capacity, Co also is strategic goods and materials, and harmful to environment.Thereby no matter for positive electrode or negative material, countries in the world have all been dropped into a large amount of man power and materials and have been researched and developed in recent years.
The oxide of Sn and Sn is (such as SnO
2) have a theoretical lithium storage content that is several times as much as commercial carbon.SnO
2Following reaction occurs in embedding lithium process:
In above-mentioned reaction, it has been generally acknowledged that reaction (1) is irreversible, by the SnO of reaction (2) generation
2Maximum reversible capacity up to 780mAh/g.SnO
2The characteristic that not only has high power capacity, its density (～6.0g/cm
3) more than the height of carbon, thereby it is as lithium ion battery negative material very advantageous on the volume capacity density that improves battery, especially with battery such as high power capacity such as grade very important meaning is arranged for large car.But Sn is at the embedding lithium and take off the volumetric expansion that occurs in the lithium process and can reach 300%, and this makes its cyclical stability relatively poor.Because the Li that reaction (1) produces
2O plays mitigation to the volumetric expansion of Sn in the removal lithium embedded process in the reaction (2) to a certain extent, thereby than Sn metal, SnO
2Cyclical stability slightly good, but this also is not enough to obtain to satisfy the cyclical stability of instructions for use.Thereby seek the preparation of simple method and have high capacity density and long-life SnO concurrently
2Negative material is for realizing its application in lithium ion battery, and it is extremely important to produce high performance lithium ion battery.
Summary of the invention
In order to solve the technical problem of above-mentioned existence, first purpose of the present invention provides a kind of high capacity lithium ion cells cathode composite material, and this composite material has the characteristic of capacity height, good cycle.Second purpose of the present invention provides a kind of above-mentioned high capacity lithium ion cells cathode composite manufacture method, and the method raw material source is wide, cost is low.The 3rd purpose of the present invention is the application that improves above-mentioned high capacity lithium ion cells cathode composite material.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
High capacity lithium ion cells cathode composite material, the component of this composite material are SnO
x / C or SnO
x The composite powder material of/Sn/C, 1＜
x≤ 2, wherein the content of carbon is 20～80wt.%, and the particle size of composite material is 0.5～50 micron, SnO in the composite material
x And Sn has nanometer or sub-micron particle size, described SnO
x And the Sn disperse is distributed in the carbon base body.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of method for preparing above-mentioned high capacity lithium ion cells cathode composite material, the method comprises the steps:
1) adopting tin compound and organic carbon source is raw material, the mol ratio of tin compound and organic carbon source is 5:1～1:5, raw material are dissolved in the effumability solvent, under 60～120 ℃ temperature, be stirred to solvent and substantially volatilize, should stir again product and further dry and grind and obtain the powder presoma;
2) the powder presoma is calcined; Calcining knot atmosphere is inert atmosphere, reducing atmosphere or vacuum; Calcining heat is 500～1100 ℃, and calcination time is 1～10 hour;
3) the calcining afterproduct is ground, obtain based on SnO
x / C or SnO
x The composite powder material of/Sn/C, particle size range are 0.5～50 micron.
Can be by regulating composite manufacture technique and parameter thereof, the content ratio of tin oxide and Sn and carbon in the adjustable composite material in the above-mentioned technique.Calcine in 500～700 ℃ of inert atmospheres and all can form SnO in 3～5 hours
2/ C composite material, SnO
2Particle size is tiny, and more evenly is embedded in the carbon base body SnO in the composite material
2Mainly exist with the form of amorphous state with carbon.Part SnO is arranged when calcining more than 800oC
2Become metal Sn by the carbon in-situ reducing, obtain SnO
2/ Sn/C composite material.The Sn crystallinity is better in the composite material, SnO
2Still mainly exist with the form of amorphous state with carbon, and carbon content has largely increase in the gained composite material.
As further improvement, described nano-graphite or CNT (carbon nano-tube) of in the preparation process of material and solvent solution, adding 5～30wt.% high conductivity.
As preferably, above-mentioned organic carbon source comprises organic acid, carbohydrate and polymer class.Be selected from citric acid, laurate, sucrose, glucose, polyvinyl alcohol, the inferior ethene of poly-two fluorine, polyethylene and the polytetrafluoroethylene one or more as preferred again, above-mentioned organic carbon source.
As preferably, above-mentioned tin compound is selected from one or more in butter of tin, stannous chloride, potassium stannate and STANNOUS SULPHATE CRYSTALLINE and their crystalline hydrate.
As preferably, above-mentioned effumability solvent is selected from one or more in water, ethanol and the acetone.
As further improvement, described step 1) in tin compound and organic carbon source are dissolved in described effumability solvent, stir certain hour and form gel under 60～100 ℃ temperature, and the gel oven dry is obtained xerogel, xerogel obtains described powder presoma through grinding.As preferably, above-mentioned tin compound is selected one or more in butter of tin and stannous chloride and their crystalline hydrate, and organic carbon source is selected citric acid.
In order to realize the 3rd above-mentioned purpose, the present invention has adopted following technical scheme:
Lithium ion battery, the negative pole of this lithium ion battery adopts above-mentioned composite material.
The present invention preparation based on SnO
2/ C and SnO
2The advantages such as the composite material of/Sn/C has the controlled easy row of preparation method, and the raw material source is wide.SnO in the composite material
2Have nanometer and sub-micron particle size with Sn, disperse is distributed in the carbon base body.Because the SnO of nano particle and submicron-scale
2In the removal lithium embedded process, have less strain with Sn, can reduce to a certain extent its efflorescence.Carbon base body not only plays good buffering SnO in the cyclic process of electrode
2With the effect of the volumetric expansion of Sn in the removal lithium embedded process, also stoped SnO
2With the reunion of Sn nano particle in the removal lithium embedded cyclic process.Carbon base body and nano graphite carbon and/or the CNT (carbon nano-tube) of adding as required have good conductivity, have improved SnO in cyclic process
2Between and electrically contacting between Sn, improved the electronic conductivity of material.Carbon base body itself has certain lithium storage content simultaneously.Therefore the present invention obtains has nanometer and sub-micron SnO
2And the sandwich that the Sn particle dispersion is distributed in carbon base body can give full play to the high capacity characteristics of tin-oxide, and makes again material have good electrochemistry cycle performance.
The present invention is owing to adopted above-mentioned technical scheme, and composite material of the present invention is 430～650mAh/g as the first reversible capacity of lithium ion battery negative material, through initial several times or after tens circulations, material list reveals good cyclical stability.Owing to contain the SnO of a great deal of in the composite material
2Or doublely contain a certain amount of Sn, and SnO
2With the density of Sn respectively up to 6.0g/cm
3And 7.3g/cm
3, be 2～3 times of carbon density, thereby composite material can obviously improve the volume capacity of battery as lithium ion battery negative material.
Description of drawings
Fig. 1 be embodiment 1 obtain based on SnO
2ESEM pattern after the composite material of/C grinds.
Fig. 2 be embodiment 1 obtain based on SnO
2The high-resolution-ration transmission electric-lens pattern of the composite material of/C demonstrates nano SnO
2Particle dispersion is distributed in the carbon base body.
Fig. 3 be embodiment 1 obtain based on SnO
2The composite material of/C is as the circulation volume figure of lithium ion battery negative material.
Fig. 4 be embodiment 2 obtain based on SnO
2The high-resolution projection Electronic Speculum pattern of the composite material of/Sn/C demonstrates nano SnO
2Be distributed in the carbon base body with nanometer Sn particle dispersion.
Fig. 5 be embodiment 2 obtain based on SnO
2The composite material of/Sn/C is as the circulation volume figure of lithium ion battery negative material.
Fig. 6 be embodiment 3 obtain based on SnO
2ESEM pattern after the composite material of/C grinds.
Fig. 7 be embodiment 3 obtain based on SnO
2The transmission electron microscope pattern of the composite material of/C, wherein under the suitable contrast, relatively grayish matrix is carbon, and the particle of Dark grey is the oxide of tin relatively, and visible Nano granules of stannic oxide disperse is distributed on the carbon base body.
Fig. 8 be embodiment 3 obtain based on SnO
2The high-resolution-ration transmission electric-lens pattern of the composite material of/C is SnO in the white circle wherein
2Particle.
Embodiment
The present invention may be better understood for following examples, but the present invention is not limited to following examples.
Embodiment 1
Taking by weighing a certain amount of mol ratio is the citric acid (C of 2:1
6H
8O
7H
2O) and butter of tin (SnCl
45H
2O) form solution take distilled water as solvent, then this solution is stirred until moisture volatilizees substantially the formation colloid at the 80oC lower magnetic force.Should glue stir to grind after product is dried in vacuum drying chamber and obtain the powder presoma.Again this powder presoma was calcined 4 hours through 700oC under nitrogen atmosphere, obtained based on SnO
2/ C composite material, carbon content is 38wt% in the composite material.Composite material is ground, be used for lithium ion battery negative material, be under the condition of 78mA/g at discharging current, the first reversible capacity of electrode reaches 650mAh/g, after tens of times initial circulations, material list reveals good cyclical stability, and Capacitance reserve has more than the 400mAh/g after 70 circulations.
Embodiment 2
Taking by weighing a certain amount of mol ratio is the citric acid (C of 2:1
6H
8O
7H
2O) and butter of tin (SnCl
45H
2O) be dissolved in distilled water, then stir until moisture volatilizees substantially the formation colloid at the 80oC lower magnetic force.Should glue stir to grind after product is dried in vacuum drying chamber and obtain the powder presoma.This powder is driven body entirely under nitrogen atmosphere, calcined 4 hours through 900oC, obtain based on SnO
2The composite material of/Sn/C, carbon content is 49wt% in the composite material.Composite material being ground, be used for lithium ion battery negative material, is under the condition of 78mA/g in measuring current, and the first reversible capacity of electrode is 430mAh/g, and material list reveals excellent cyclical stability.
Embodiment 3
Take by weighing glucose and butter of tin (SnCl that a certain amount of mol ratio is 1:1
45H
2O) be dissolved in distilled water, then stir until moisture volatilizees substantially at the 80oC lower magnetic force.Should stir to grind after product is dried in vacuum drying chamber and obtain the powder presoma.This powder is driven body entirely under nitrogen atmosphere, calcined 4 hours through 700oC, obtain based on SnO
2The composite material of/C.Composite material is ground, be used for lithium ion battery negative material, demonstrate good cyclical stability.
Embodiment 4
Take by weighing glucose and the stannous chloride that a certain amount of mol ratio is 3:1 and be dissolved in distilled water, and in this solution, add the nano-graphite of 5wt.%, then stir until moisture volatilizees substantially at the 80oC lower magnetic force.Should stir to grind after product is dried in vacuum drying chamber and obtain the powder presoma.This powder is driven body entirely under nitrogen atmosphere, calcined 4 hours through 700oC, obtain based on SnO
2The composite material of/C.Composite material is ground, be used for lithium ion battery negative material, demonstrate good cyclical stability.
Take by weighing glucose and the stannous chloride that a certain amount of mol ratio is 3:1 and be dissolved in distilled water, and add the nano-graphite of 5wt.%, then under 80oC, stir until moisture volatilizees substantially.Should stir to grind after product is dried in vacuum drying chamber and obtain the powder presoma.This powder is driven body entirely under nitrogen atmosphere, calcined 4 hours through 850oC, obtain based on SnO
2The composite material of/Sn/C.Composite material is ground, be used for lithium ion battery negative material, demonstrate good cyclical stability.
Embodiment 6
Taking by weighing a certain amount of mol ratio is that the inferior ethene of two fluorine of gathering of 2:1 and STANNOUS SULPHATE CRYSTALLINE are dissolved in ethanol water, then stirs until moisture volatilizees substantially under 80oC.Should stir to grind after product is dried in vacuum drying chamber and obtain the powder presoma.This powder is driven body entirely under nitrogen atmosphere, calcined 3 hours through 600oC, obtain based on SnO
2The composite material of/C.Composite material is ground, be used for lithium ion battery negative material, demonstrate good cyclical stability.
Claims (4)
1. high capacity lithium ion cells cathode composite material, it is characterized in that: the component of this composite material is SnO
x / C or SnO
x The composite powder material of/Sn/C, 1＜
x≤ 2, wherein the content of carbon is 20～80wt.%, and the particle size of composite material is 0.5～50 micron, SnO in the composite material
x And Sn is 2 nanometers～1 micron, described SnO
x And the Sn disperse is distributed in the carbon base body; Above-mentioned anode material adopts following step to prepare:
1) adopting tin compound and organic carbon source is raw material, the mol ratio of tin compound and organic carbon source is 5:1～1:5, tin compound and organic carbon source are dissolved in effumability solvent or water, under 60～100 ℃ temperature, stir certain hour and form gel, and gel oven dry obtained xerogel, xerogel obtains the powder presoma through grinding;
2) the powder presoma is calcined; Calcining knot atmosphere is inert atmosphere, reducing atmosphere or vacuum; Calcining heat is 500～1100 ℃, and calcination time is 1～10 hour;
3) the calcining afterproduct is ground, obtain based on SnO
x / C or SnO
x The composite powder material of/Sn/C, particle size range are 0.5～50 micron;
Described tin compound is selected one or more in butter of tin and stannous chloride and their crystalline hydrate, and organic carbon source is selected citric acid; The effumability solvent is selected from one or more in ethanol and the acetone.
2. a method for preparing high capacity lithium ion cells cathode composite material as claimed in claim 1 is characterized in that the method comprises the steps:
1) adopting tin compound and organic carbon source is raw material, the mol ratio of tin compound and organic carbon source is 5:1～1:5, tin compound and organic carbon source are dissolved in described effumability solvent or water, under 60～100 ℃ temperature, stir certain hour and form gel, and gel oven dry obtained xerogel, xerogel obtains described powder presoma through grinding;
2) the powder presoma is calcined; Calcining knot atmosphere is inert atmosphere, reducing atmosphere or vacuum; Calcining heat is 500～1100 ℃, and calcination time is 1～10 hour;
3) the calcining afterproduct is ground, obtain based on SnO
x / C or SnO
x The composite powder material of/Sn/C, particle size range are 0.5～50 micron;
Described tin compound is selected one or more in butter of tin and stannous chloride and their crystalline hydrate, and organic carbon source is selected citric acid; The effumability solvent is selected from one or more in ethanol and the acetone.
3. method according to claim 2 is characterized in that: nano-graphite or the CNT (carbon nano-tube) of adding 5～30wt.% high conductivity in the preparation process of raw material and solvent solution.
4. lithium ion battery, it is characterized in that: the negative pole of this lithium ion battery adopts composite material as claimed in claim 1.
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| CN110336015B (en) * | 2019-07-15 | 2020-12-18 | 首都师范大学 | Preparation method of carbon-coated tin and tin-iron alloy lithium ion battery cathode material |
| CN110697762B (en) * | 2019-10-15 | 2022-03-29 | 哈尔滨工业大学 | Hollow structure Sn/SnO2Preparation method of @ C lithium ion battery negative electrode material |
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