CN103811730A - High-capacity lithium ion battery composite negative electrode material and preparation method thereof - Google Patents

High-capacity lithium ion battery composite negative electrode material and preparation method thereof Download PDF

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CN103811730A
CN103811730A CN201210444927.5A CN201210444927A CN103811730A CN 103811730 A CN103811730 A CN 103811730A CN 201210444927 A CN201210444927 A CN 201210444927A CN 103811730 A CN103811730 A CN 103811730A
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oxalate
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lithium ion
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CN103811730B (en
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石先兴
葛民民
吕豪杰
谭东庆
陈军
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Wanxiang 123 Co Ltd
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Wanxiang Group Corp
Wanxiang Electric Vehicle Co Ltd
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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
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Composite Materials (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a high-capacity lithium ion battery composite negative electrode material and a preparation method thereof, wherein problems of low charging-discharging specific capacity and poor cycle performance of application of the existing carbon material as the lithium ion battery negative electrode material are solved. According to the present invention, the high-capacity lithium ion battery composite negative electrode material is a composite powder material comprising a component Si/SnC2O4 or Si/SnC2O4/C, wherein silicon powder, a soluble stannous salt and a soluble oxalate are subjected to a mixing reaction, the obtained solid is dried to obtain Si/SnC2O4, a carbon material is added according to a ratio, and ball milling is performed to obtain Si/SnC2O4/C; the particle size of the material is 0.5-30 mum, a mass ratio of Si to SnC2O4 is 1:10-10:1 in Si/SnC2O4 or Si/SnC2O4/C, and the mass percent content of the elemental carbon in Si/SnC2O4/C is 5-90%; and the high-capacity lithium ion battery composite negative electrode material has characteristics of high electricity capacity, good cycle performance and good stability, and the preparation method has characteristics of simple process step, easy operation and low production cost.

Description

Composite negative pole material of a kind of high-capacity lithium ion cell and preparation method thereof
 
Technical field
The present invention relates to technical field of lithium ion, especially relate to composite negative pole material of a kind of high-capacity lithium ion cell and preparation method thereof.
 
Background technology
Along with the fast development of pure electric automobile and mixed power electric car, for high-energy-density, the demand of high security lithium ion battery is very urgent, current business-like power-type lithium ion battery negative material is generally graphite, the material with carbon elements such as acetylene black, but material with carbon element charging and discharging capacity low (theoretical capacity 372mAh/g), and develop and approached theoretical value at present, on the other hand, the possibility that positive electrode makes a breakthrough is in a short time less, therefore, a large amount of research has turned to searching can substitute the Novel anode material of material with carbon element, to realize the high safety of lithium ion battery, large capacity and long circulation life.
Application publication number CN102208638A, the patent of Shen Qing Publication day 2011.10.05 discloses a kind of high capacity lithium ion cells cathode composite material and preparation method thereof, the component of this composite material is SnOx/C or SnOx/Sn/C, 1 < X≤2, wherein, the content of carbon is 20 ~ 80wt%, the particle size of composite material is 0.5 ~ 50 micron, in composite material, SnOx and Sn are 2 nanometer ~ 1 micron, the main substance that in this anode material, lithium ion embeds/deviates from is SnOx and Sn, although the reversible capacity first of this anode material can reach 430 ~ 650mAh/g, but after tens of circulations, capacity only remains on 300 mAh/g left and right, with respect to material with carbon element as negative material (theoretical capacity 372mAh/g), it is not remarkable that its capacity improves effect, secondly, SnOx and Sn all need to obtain by high-temperature calcination under oxygen free condition, preparation condition requires very strict, and cost is also very high.
 
Summary of the invention
The present invention is low as power-type lithium ion battery negative material charging and discharging capacity in order to solve existing material with carbon element, the problem that cycle performance is poor, a kind of composite negative pole material of high-capacity lithium ion cell is provided, and the capacitance of this composite negative pole material is large, and cycle performance and stability are good.
The present invention also provides a kind of preparation method of composite negative pole material of capacity lithium ion battery, and this preparation method's processing step is simple, and reaction condition requires low, easy operating, and production cost is low.
To achieve these goals, the present invention is by the following technical solutions:
A composite negative pole material for high-capacity lithium ion cell, described composite negative pole material is that component is Si/SnC 2o 4or Si/SnC 2o 4the composite powder material of/C, the particle diameter of this composite powder material is 0.5 ~ 30 μ m, at Si/SnC 2o 4or Si/SnC 2o 4in/C, Si and SnC 2o 4mass ratio be 1:10 ~ 10:1, Si/SnC 2o 4in/C, the quality percentage composition of carbon simple substance is 5 ~ 90%.The main substance that the present invention embeds/deviates from as lithium ion using Si, in the process discharging and recharging, can form the silicon-lithium alloy very high containing lithium amount with lithium ion, embedding lithium theoretical capacity is up to 4200mAh/g, far away higher than the charging and discharging capacity (theoretical capacity 372mAh/g) of material with carbon element, but after silicon-lithium alloy embedding lithium, cubical expansivity is up to 300%, far away higher than material with carbon element 10%, this can make electrode material efflorescence, active material comes off from collector, lose and contact with collector, cause circulating battery stability very poor, the present invention SnC 2o 4closely parcel Si, to stablize the structure of Si, SnC 2o 4can not only cushion the change in volume of Si while discharging and recharging, can stop again the reunion of Si in charge and discharge process simultaneously, avoid Si that the structure heavy damage of negative material occurs to be caused to the irreversible transformation of unordered form by crystalline state in the process that embeds/deviate from lithium ion, thereby greatly reduce the efflorescence of composite negative pole material, carbon is in order to improve the conductivity of whole composite negative pole material, improve electronic conductivity, carbon itself also has certain lithium storage content simultaneously.Therefore composite negative pole material of the present invention not only has great capacitance, and can be in charge and discharge process holding structure stable, cycle performance and good stability.
A preparation method for the composite negative pole material of high-capacity lithium ion cell, comprises the following steps:
(1) take a certain amount of silica flour, by Si/SnC 2o 4or Si/SnC 2o 4si and SnC in/C 2o 4mass ratio be that 1:10 ~ 10:1 calculates SnC 2o 4required quality, according to the SnC calculating 2o 4required quality, generates SnC by solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning, metering solubility tin salt, is added to the water silica flour and solubility tin salt, obtains suspension-turbid liquid.Silica flour and solubility tin salt are added to the water, as long as the amount of water is dissolved solubility tin salt completely, silica flour dispersibles in water simultaneously, the composite negative pole material good uniformity obtaining like this, and parcel is evenly.
(2) generate SnC according to solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning, by Sn 2+with C 2o 4 2-mol ratio be 1:1.1 ~ 1.3, metering Soluble oxalate salt, by soluble in water Soluble oxalate salt, obtains Soluble oxalate salting liquid.Control Sn 2+with C 2o 4 2-mol ratio be 1:1.1 ~ 1.3, make Soluble oxalate salt excessive, guarantee that solubility tin salt can react completely, so that the SnC that can obtain calculating 2o 4required quality, can guarantee that solubility tin salt reacts completely simultaneously, can avoid again the excess waste of Soluble oxalate salt to control cost, and the amount of water there is not specific (special) requirements, as long as guarantee that Soluble oxalate salt dissolves completely.
(3) Soluble oxalate salting liquid is poured in suspension-turbid liquid, the pH that regulates whole reaction system is 0.5 ~ 3 rear continuous stirring 1 ~ 3h, obtains reactant liquor.The reaction principle of this step is: Sn 2++ C 2o 4 2-=SnC 2o 4↓, this reaction stirring reaction at normal temperatures and pressures, the SnC of generation 2o 4disperse is distributed in Si powder particles, and Si powder is closely wrapped up, and this process step is simple, and reaction condition requirement is low, and production cost is low.
(4), by reactant liquor Separation of Solid and Liquid, the solid obtaining obtains Si/SnC after washing, oven dry 2o 4.
(5) press Si/SnC 2o 4in/C, the quality percentage composition of carbon simple substance is 5 ~ 90% metering material with carbon elements, by material with carbon element and the Si/SnC obtaining 2o 4rotating speed high speed ball milling 1 ~ 3h with 100 ~ 300rpm after mixing obtains Si/SnC 2o 4/ C.Adding material with carbon element is mainly that material with carbon element itself also has certain lithium storage content simultaneously in order to improve conductivity, and high speed ball milling can make material with carbon element be evenly dispersed in Si/SnC 2o 4in, can make again the particle diameter of composite negative pole material keep evenly.
As preferably, in step (1), the particle diameter of silica flour is 0.1 ~ 10 μ m.The particle diameter of silica flour is 0.1 ~ 10 μ m, is convenient to SnC 2o 4tight parcel, also can avoid silica flour to reunite, guarantee that the composite negative pole material particle diameter that obtains is within the scope of 0.5 ~ 30 μ m simultaneously.
As preferably, described silica flour makes by the following method: be the silicon ball of 20 ~ 30 μ m by particle diameter, in ethanol medium, to dry at 100 ~ 110 ℃ after rotating speed high speed ball milling 2 ~ 3h of 300 ~ 400rpm.
As preferably, described solubility tin salt is stannous chloride or stannous sulfate.
As preferably, described Soluble oxalate salt is alkaline metal oxalate.
As preferably, described alkaline metal oxalate is potassium oxalate, sodium oxalate or ammonium oxalate.
As preferably, after in step (3), Soluble oxalate salting liquid is poured in suspension-turbid liquid, regulating the pH of whole reaction system by acid solution is 0.5 ~ 3.After in Soluble oxalate salting liquid is poured suspension-turbid liquid into, regulating the pH of whole reaction system by acid solution is 0.5 ~ 3, keep whole reaction system for acid, the one, can keep the dissolubility of solubility tin salt, the 2nd, can promote reaction to carry out, there is no particular limitation for acid solution, generally uses hydrochloric acid, sulfuric acid all can.
As preferably, while oven dry in step (4), bake out temperature is 80 ~ 100 ℃.Temperature is too low, and drying efficiency is low, excess Temperature, SnC 2o 4easily decompose, baking temperature is 80 ~ 100 ℃, has both guaranteed drying efficiency, can avoid again SnC 2o 4decomposition.
As preferably, described in step (5), material with carbon element is conductive carbon black, graphite, acetylene black or carbon nano-tube.
Therefore, the present invention has following beneficial effect:
(1) there is great capacitance, cycle performance and good stability;
(2) processing step is simple, and reaction condition requires low, easy operating, and cost is low.
Accompanying drawing explanation
Fig. 1 is the Si/SnC that embodiment 1 obtains 2o 4sEM figure.
Fig. 2 is the Si/SnC that embodiment 1 obtains 2o 4cycle performance curve chart.
Fig. 3 is the Si/SnC that embodiment 2 obtains 2o 4the SEM figure of/C.
Fig. 4 is the Si/SnC that embodiment 2 obtains 2o 4the cycle performance curve chart of/C.
 
Embodiment
Below by embodiment, the present invention will be further described.
In the present invention, if not refer in particular to, all percentage is unit of weight, and all devices and raw material all can be buied from market or the industry is conventional, and the method in following embodiment, if no special instructions, is this area conventional method.
 
Embodiment 1
(1) be the silicon ball of 20 ~ 30 μ m by particle diameter, in ethanol medium, take after the rotating speed high speed ball milling 3h of 300rpm, at 100 ℃, dry particle diameter as the silica flour of 0.1 ~ 10 μ m, take the silica flour after 20g ball milling, by Si/SnC 2o 4middle Si and SnC 2o 4mass ratio be that 1:1 calculates SnC 2o 4required quality, needs 20g SnC 2o 4, according to the SnC calculating 2o 4required quality, generates SnC by solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning metering solubility tin salt, wherein, solubility tin salt is stannous chloride, Soluble oxalate salt is sodium oxalate, obtains 18.4g stannous chloride, the stannous chloride that silica flour and the First Astronautic Research Institute for Measurement and Test are obtained adds in 60g water, obtains 98.4g suspension-turbid liquid.
(2) generate SnC according to solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning, by Sn 2+with C 2o 4 2-mol ratio be 1:1.1, metering Soluble oxalate salt (sodium oxalate), obtain 14.3g sodium oxalate, Soluble oxalate salt (sodium oxalate) is dissolved in 70g water, obtain 84.3g Soluble oxalate salt (sodium oxalate) solution.
(3) Soluble oxalate salt (sodium oxalate) solution is poured in suspension-turbid liquid, and to regulate the pH of whole reaction system with sulfuric acid be 2 rear continuous stirring 2h, obtain reactant liquor.
(4), by reactant liquor Separation of Solid and Liquid, the solid obtaining obtains the Si/SnC that particle diameter is 0.5 ~ 30 μ m after washing, oven dry 2o 4, bake out temperature is 90 ℃.
The Si/SnC obtaining 2o 4sEM scheme as shown in Figure 1, as can be seen from Figure 1, Si is by SnC 2o 4after coated, form ganoid bulky grain structure.
By the Si/SnC obtaining 2o 4for lithium ion battery negative, at 25 ℃, the charge-discharge magnification of 0.1C, carries out cycle performance test under the condition that voltage is 0.01 ~ 2.0V, and the cycle performance curve chart obtaining as shown in Figure 2.
As can be seen from Figure 2, Si/SnC 2o 4reversible capacity first as lithium ion battery negative material can reach 2200mAh/g, reversible charge/discharge capacity after 30 circulations is still up to 1500mAh/g, charging and discharging capacity after stable exceeds nearly 4 times than the theoretical charging and discharging capacity 372mAh/g of material with carbon element, shows Si/SnC of the present invention 2o 4not only there is great capacitance, and cycle performance and stability very outstanding.
 
Embodiment 2
All the other steps of embodiment 2 are all identical with embodiment 1, and difference is, makes Si/SnC 2o 4after, by Si/SnC 2o 4in/C, the quality percentage composition of carbon simple substance is 10% metering material with carbon element, and material with carbon element is conductive carbon black, by material with carbon element and the Si/SnC obtaining 2o 4after mixing, after the rotating speed high speed ball milling 3h of 100rpm, obtain the Si/SnC of particle diameter as 0.5 ~ 30 μ m 2o 4/ C.
The Si/SnC obtaining 2o 4the SEM of/C schemes as shown in Figure 3, and as can be seen from Figure 3, Si is by SnC 2o 4after coated, form ganoid bulky grain structure, C(flaky substance) be dispersed in Si/SnC 2o 4between (particle).
By the Si/SnC obtaining 2o 4/ C is for lithium ion battery negative, and at 25 ℃, the charge-discharge magnification of 0.1C, carries out cycle performance test under the condition that voltage is 0.01 ~ 2.0V, and the cycle performance curve chart obtaining as shown in Figure 4.
As can be seen from Figure 4, Si/SnC 2o 4reversible capacity first as lithium ion battery negative material can reach 1900mAh/g, reversible charge/discharge capacity after 30 circulations is still up to 1200mAh/g, charging and discharging capacity after stable exceeds more than 3 times than the theoretical charging and discharging capacity 372mAh/g of material with carbon element, shows Si/SnC of the present invention 2o 4/ C not only has great capacitance, and cycle performance and stability also very outstanding.
 
Embodiment 3
(1) be the silicon ball of 20 ~ 30 μ m by particle diameter, in ethanol medium, take after the rotating speed high speed ball milling 2.5h of 360rpm, at 105 ℃, dry particle diameter as the silica flour of 0.1 ~ 10 μ m, take the silica flour after 100g ball milling, by Si/SnC 2o 4middle Si and SnC 2o 4mass ratio be that 1:10 calculates SnC 2o 4required quality, needs 1000g SnC 2o 4, according to the SnC calculating 2o 4required quality, generates SnC by solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning metering solubility tin salt, wherein, solubility tin salt is stannous sulfate, Soluble oxalate salt is potassium oxalate, obtains 1038.7g stannous sulfate, the stannous sulfate that silica flour and the First Astronautic Research Institute for Measurement and Test are obtained adds in 4200g water, obtains 5338.7g suspension-turbid liquid.
(2) generate SnC according to solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning, by Sn 2+with C 2o 4 2-mol ratio be 1:1.2, metering Soluble oxalate salt (potassium oxalate), obtain 963.7g potassium oxalate, Soluble oxalate salt (potassium oxalate) is dissolved in 4000g water, obtain 4963.7g Soluble oxalate salt (potassium oxalate) solution.
(3) Soluble oxalate salt (potassium oxalate) solution is poured in suspension-turbid liquid, and to regulate the pH of whole reaction system with hydrochloric acid be 0.5 rear continuous stirring 3h, obtain reactant liquor.
(4), by reactant liquor Separation of Solid and Liquid, the solid obtaining obtains the Si/SnC that particle diameter is 0.5 ~ 30 μ m after washing, oven dry 2o 4, bake out temperature is 80 ℃.
The Si/SnC that the present embodiment obtains 2o 4sEM figure similar with Fig. 1, Fig. 2 respectively with cycle performance curve chart, therefore do not enumerate and repeat at this.
 
Embodiment 4
All the other steps of the present embodiment are all identical with embodiment 3, and difference is, makes Si/SnC 2o 4after, by Si/SnC 2o 4in/C, the quality percentage composition of carbon simple substance is 5% metering material with carbon element, and material with carbon element is acetylene black, by material with carbon element and the Si/SnC obtaining 2o 4after mixing, after the rotating speed high speed ball milling 2h of 200rpm, obtain the Si/SnC of particle diameter as 0.5 ~ 30 μ m 2o 4/ C.
The Si/SnC that the present embodiment obtains 2o 4the SEM figure of/C is similar with Fig. 3, Fig. 4 respectively with cycle performance curve chart, therefore do not enumerate and repeat at this.
 
Embodiment 5
(1) be the silicon ball of 20 ~ 30 μ m by particle diameter, in ethanol medium, take after the rotating speed high speed ball milling 2h of 400rpm, at 110 ℃, dry particle diameter as the silica flour of 0.1 ~ 10 μ m, take the silica flour after 500g ball milling, by Si/SnC 2o 4middle Si and SnC 2o 4mass ratio be that 10:1 calculates SnC 2o 4required quality, needs 50g SnC 2o 4, according to the SnC calculating 2o 4required quality, generates SnC by solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning metering solubility tin salt, wherein, solubility tin salt is stannous chloride, Soluble oxalate salt is ammonium oxalate, obtains 45.9g stannous chloride, and silica flour and solubility tin salt are added in 210g water, obtains 760g suspension-turbid liquid.
(2) generate SnC according to solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning, by Sn 2+with C 2o 4 2-mol ratio be 1:1.3, metering Soluble oxalate salt (ammonium oxalate), obtain 39g ammonium oxalate, Soluble oxalate salt (ammonium oxalate) is dissolved in 1800g water, obtain 1839g Soluble oxalate salt (ammonium oxalate) solution.
(3) Soluble oxalate salt (ammonium oxalate) solution is poured in suspension-turbid liquid, and to regulate the pH of whole reaction system with hydrochloric acid be 3 rear continuous stirring 1h, obtain reactant liquor.
(4), by reactant liquor Separation of Solid and Liquid, the solid obtaining obtains the Si/SnC that particle diameter is 0.5 ~ 30 μ m after washing, oven dry 2o 4, bake out temperature is 100 ℃.
The Si/SnC that the present embodiment obtains 2o 4sEM figure similar with Fig. 1, Fig. 2 respectively with cycle performance curve chart, therefore do not enumerate and repeat at this.
 
Embodiment 6
All the other steps of the present embodiment are all identical with embodiment 5, and difference is, makes Si/SnC 2o 4after, by Si/SnC 2o 4in/C, the quality percentage composition of carbon simple substance is 90% metering material with carbon element, and material with carbon element is carbon nano-tube, by material with carbon element and the Si/SnC obtaining 2o 4after mixing, after the rotating speed high speed ball milling 1h of 300rpm, obtain the Si/SnC of particle diameter as 0.5 ~ 30 μ m 2o 4/ C.
The Si/SnC that the present embodiment obtains 2o 4the SEM figure of/C is similar with Fig. 3, Fig. 4 respectively with cycle performance curve chart, therefore do not enumerate and repeat at this.
 
Above-described embodiment is preferably scheme of one of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim records.

Claims (10)

1. a composite negative pole material for high-capacity lithium ion cell, is characterized in that, described composite negative pole material is that component is Si/SnC 2o 4or Si/SnC 2o 4the composite powder material of/C, the particle diameter of this composite powder material is 0.5 ~ 30 μ m, at Si/SnC 2o 4or Si/SnC 2o 4in/C, Si and SnC 2o 4mass ratio be 1:10 ~ 10:1, Si/SnC 2o 4in/C, the quality percentage composition of carbon simple substance is 5 ~ 90%.
2. a preparation method for the composite negative pole material of high-capacity lithium ion cell as claimed in claim 1, is characterized in that, comprises the following steps:
(1) take a certain amount of silica flour, by Si/SnC 2o 4or Si/SnC 2o 4si and SnC in/C 2o 4mass ratio be that 1:10 ~ 10:1 calculates SnC 2o 4required quality, according to the SnC calculating 2o 4required quality, generates SnC by solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning, metering solubility tin salt, is added to the water silica flour and solubility tin salt, obtains suspension-turbid liquid;
(2) generate SnC according to solubility tin salt and Soluble oxalate reactant salt 2o 4chemical reaction proportioning, by Sn 2+with C 2o 4 2-mol ratio be 1:1.1 ~ 1.3, metering Soluble oxalate salt, by soluble in water Soluble oxalate salt, obtains Soluble oxalate salting liquid;
(3) Soluble oxalate salting liquid is poured in suspension-turbid liquid, the pH that regulates whole reaction system is 0.5 ~ 3 rear continuous stirring 1 ~ 3h, obtains reactant liquor;
(4), by reactant liquor Separation of Solid and Liquid, the solid obtaining obtains Si/SnC after washing, oven dry 2o 4;
(5) press Si/SnC 2o 4in/C, the quality percentage composition of carbon simple substance is 5 ~ 90% metering material with carbon elements, by material with carbon element and the Si/SnC obtaining 2o 4rotating speed high speed ball milling 1 ~ 3h with 100 ~ 300rpm after mixing obtains Si/SnC 2o 4/ C.
3. preparation method according to claim 2, is characterized in that, in step (1), the particle diameter of silica flour is 0.1 ~ 10 μ m.
4. preparation method according to claim 3, is characterized in that, described silica flour makes by the following method: be the silicon ball of 20 ~ 30 μ m by particle diameter, in ethanol medium, to dry at 100 ~ 110 ℃ after rotating speed high speed ball milling 2 ~ 3h of 300 ~ 400rpm.
5. preparation method according to claim 2, is characterized in that, described solubility tin salt is stannous chloride or stannous sulfate.
6. preparation method according to claim 2, is characterized in that, described Soluble oxalate salt is alkaline metal oxalate.
7. preparation method according to claim 6, is characterized in that, described alkaline metal oxalate is potassium oxalate, sodium oxalate or ammonium oxalate.
8. according to the preparation method described in claim 2 or 6 or 7, it is characterized in that, after in step (3), Soluble oxalate salting liquid is poured in suspension-turbid liquid, regulating the pH of whole reaction system by acid solution is 0.5 ~ 3.
9. preparation method according to claim 2, is characterized in that, while oven dry in step (4), bake out temperature is 80 ~ 100 ℃.
10. preparation method according to claim 2, is characterized in that, described in step (5), material with carbon element is conductive carbon black, graphite, acetylene black or carbon nano-tube.
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Cited By (5)

* Cited by examiner, † Cited by third party
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CN104600247A (en) * 2014-12-31 2015-05-06 山东玉皇新能源科技有限公司 Sulfur-carbon composite positive electrode material for lithium-sulfur battery and preparation method of sulfur-carbon composite positive electrode material
CN105895859A (en) * 2016-04-25 2016-08-24 陈友根 Preparation method of high-specific capacity lithium ion battery anode material
CN109860526A (en) * 2018-11-19 2019-06-07 昆明理工大学 The preparation method of graphite type material doping metals oxalates lithium battery composite negative pole material
CN112117457A (en) * 2020-09-18 2020-12-22 昆明理工大学 Preparation method of carbon nano tube doped tubular tin oxalate negative electrode material
CN114094084A (en) * 2021-11-24 2022-02-25 昆明理工大学 Preparation method and application of metal oxalate-graphite composite electrode material

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