CN103872296A - Method for preparing lithium ion battery porous silicon composite cathode material by industrial silicon waste material - Google Patents
Method for preparing lithium ion battery porous silicon composite cathode material by industrial silicon waste material Download PDFInfo
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- 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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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention belongs to the electrochemistry field, and is in particular to reutilization of lithium ion battery cathode material and siliceous industrial waste material. Silane and trichlorosilane are important raw materials for preparing an organosilicon polymer and polysilicon, and the siliceous industrial waste material output generated during a production process is huge. Usually, the cooper (residual catalyst) in the waste material is recovered, which is imbedded as a soil. The industrial waste material is subjected to the processes of washing, sorting, pretreating, and then carbon cladding is carried out, the obtained porous silicon/carbon/copper composite material is taken as a cathode material of the lithium ion battery. In the material, silicon has abundant pore structure, its porous structure and the coated carbon layer can reduce the volume expansion and contraction of silicon during a lithiation process, copper and the coated carbon layer can increase the conductivity of a silicon-based cathode material, so that the specific capacity and cycle performance of the silicon-based cathode material are increased. The method for preparing the lithium ion battery porous silicon composite cathode material by the industrial silicon waste material can realize the reutilization of the industrial waste material, and provides a cheap and practical new approach for high specific capacity silicon cathode material of the lithium ion battery.
Description
Technical field
The present invention relates to produce the recycling of siliceous industrial waste and the preparation of porous silicon composite material in silane and trichlorosilane preparation process, gained porous silicon composite material is applicable to lithium ion battery or lithium-sulfur cell negative material, belongs to electrochemical field.
Background technology
Specific energy is high, cycle life good, discharge voltage is stable, operating temperature range is wide, self-discharge rate is low, storage life is long owing to having for lithium ion battery, memory-less effect and the advantage such as nuisanceless are widely used.Along with day by day in short supply and pressure environmental pollution of traditional fossil energy increases day by day, developing green alternative energy source has become the problem of worldwide attention.And lithium ion battery is because of its above-mentioned advantage, aspect the scale energy storage of new-energy automobile and regenerative resource, there is great application prospect.
Commercial lithium-ion batteries negative pole adopts graphitized carbon (as carbonaceous mesophase spherules MCMB and CMS) material at present, and the volumetric expansion in this class material doff lithium process is substantially below 9%, and coulombic efficiency is higher, and stable circulation performance is outstanding.But the lower theory of graphite electrode storage lithium specific capacity itself makes it be difficult to make a breakthrough again, the electrode material that therefore researcher is exploring a kind of Novel high-specific capacity flexible always substitutes graphitized carbon material.The alloy type material that in negative material, Si, Sn, Al etc. and Li form, its reversible lithium storage specific capacity is far away higher than graphite negative electrodes.And wherein silicon becomes study hotspot owing to having the advantages such as the highest theoretical lithium storage content (4200mAh/g), doff lithium current potential are low, cheap.But all there is the volumetric expansion (cubical expansivity > 300%) of highly significant in pure silicon material in height embedding lithium process, consequent mechanical stress makes electrode material efflorescence gradually in cyclic process, alloy structure is destroyed, between active material and collector, electrically contact forfeiture, thereby cause cycle performance to decline.The cyclical stability that how to improve silica-base material is the research emphasis of such material.
Structural unstable shortcoming when solving silicium cathode doff lithium, improves the cycle performance of electrode, and the measure adopting at present mainly contains following several:
First be to reduce material particle size, by material nano.Nano material has that specific area is large, ion the evolving path is short, wriggling is strong and plasticity high, can alleviate to a certain extent the bulk effect of silicium cathode material, improves its chemical property.At present report silicon nanowires, nanometer rods, nanotube, nanosphere, silica-base film etc., material specific capacity and cycle performance all be improved significantly.But silicon-based nano material is more remote in addition apart from practicality, first need to overcome that preparation cost is high, complex process, the problem that is difficult to large-scale production.And nano material is unsettled on thermodynamics, easily to reunite, the stability of long-term circulation time electrode need to investigate.
Second method is by compound to silicium cathode and carbon or other nonmetallic compound.Can suppress the reunion of silicon, stress when padded coaming change in volume with the compound one side of material with carbon element; Can greatly improve on the other hand the conductivity of material; In addition, the existence of carbon-coating can also reduce the side reaction of silicon and electrolyte, improves a coulomb efficiency.The material with carbon element of application mainly contains amorphous carbon, graphite, carbonaceous mesophase spherules, carbon nano-tube, Graphene etc. at present.Buffering when nonmetallic compound compound same can provide volumetric expansion for silicon, improves electrode stability.Silicon-nonmetallic compound comprises Si oxide and other silicon-nonmetallic compounds etc.The preparation method of composite material mainly contains high temperature pyrolytic cracking (HTP), sol-gal process, high-energy ball milling method and chemical vapour deposition technique etc.To consider two problems with the compound composite material of preparing of carbon: the one, carbon add mode.How can, under comparatively simple/economic combination process, improve the performance of composite material.The 2nd, how to make carbon and silicon obtain comparatively desirable dispersion.Dispersion effect obviously has considerable influence to material property, if disperse badly, causes the reunion of silicon in material part, and material property obviously can be not very good.
The third approach is by silicon and metal composite, prepares composite material.Silicon and metal composite, can provide for the volumetric expansion of silicon on the one hand a kind of carrier of buffering, improves the stability of electrode, on the other hand, and with the compound conductivity that can reinforcing material of metal.Have multiplely with the compound metal of silicon, wherein have electro-chemical activity, also have electrochemistry inertia, the improvement of material property had to comparatively significantly effect.Such as by coating metal particles on silicon grain as Ag, Fe, Co, Cu, can significantly improve electronics contact, promotes the cyclicity of embedding lithium reaction.Same silicon/material with carbon element is the same, and silicon/metallic composite will solve the scattering problem of silicon and metal equally, how to make metal particle can be distributed to comparatively equably the surface of silicon, forms effective coating layer.Cladding process aspect, the now methods that adopt chemical vapour deposition (CVD), plating, sputter or high-energy ball milling more.
The 4th kind of method is that silicon is prepared into porous material, and the inner abundant hole of porous silica material has been reserved space for its volumetric expansion, and can reduce storage lithium time, macroscopical volumetric expansion of material, alleviates mechanical stress.But all there is raw material costliness, process complexity, produce the shortcoming of pollutant in the method for preparing at present porous silicon.
The research of silicon based anode material has obtained remarkable break-throughs, and performance has also obtained greatly improving.But its industrialization still makes little progress at present, problem demanding prompt solution is to optimize material preparation method and technique, reduces costs.
Summary of the invention
The invention provides a kind of new approaches of utilizing industrial silicon waste material to prepare lithium ion battery porous silicon composite negative pole material.Siliceous industrial waste mainly contains two sources: the one, in the preparation process of organosilan, as methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, ethyl chlorosilane, phenyl chlorosilane, phenyl trichlorosilane etc.; The 2nd, in the technique of high purity polycrystalline silicon used for solar batteries, also can produce a large amount of scrap silicons with Siemens's legal system for the process of raw material trichlorosilane.It is catalyst that these two technical processs generally all adopt copper powder, reacts to be:
In formula, n=1-3, X is Cl or Br, R is H, methyl, ethyl, propyl group, vinyl, more than one groups in phenyl.
In the preparation feedback process of organosilan, alkyl halide constantly generates silane with pasc reaction on silicon and copper catalyst contact-making surface, thereby forms many holes at silicon face, reacts finally because accumulating carbon on silicon face and halogen chlorosilane polymer stops.In the preparation feedback process of trichlorosilane, hydrogen chloride gas is continuous and pasc reaction generation trichlorosilane on silicon and copper catalyst contact-making surface, thereby forms many holes at silicon face, and reaction is equally finally because covering copper on silicon face and other impurity stop.So after reaction finishes, two kinds of sources all can produce the porous silicon waste material of cupric, carbon.
Two kinds of sources containing in scrap silicon except active ingredient porous Si, Cu, C, also contain the halide of the metal such as Fe, Al, and halosilanes, the SiHCl of absorption
3deng, in addition, also having part because of the excessive substantially unreacted bulk silicon of particle, need to remove by different pre-treatment step.
In the present invention, these siliceous industrial wastes are processed, obtained can be used for the material of lithium ion battery negative.Preparation method's step is as follows:
1. preliminary treatment: for the waste material of separate sources, use two kinds of preprocess methods, a kind of is that its pre-treatment step is 200～800 ℃ of pyrolysis silane polymers under nitrogen protection for the industrial silicon waste material that derives from preparation silane process process; Another kind is the industrial silicon waste material of preparing trichlorosilane technical process for deriving from, and its pre-treatment step is to clean with clear water, and cleaning method is immersion, extracting or stirring;
2. from preliminary treatment scrap silicon, sub-elect the particle that particle diameter is less than 1mm;
3. the material sub-electing is pulverized in ball milling or grinder to the micro mist that is less than 10 μ m for particle diameter;
4. take organic substance as carbon source, micropowder material is coated, organic mass percent example is 1%～40%;
5. in high temperature furnace, the micropowder material heat treated coated to carbon source, heat treatment temperature is 400～1000 ℃, heat treatment time is 0.1～72h, makes organic carbon and improves conductivity, obtains porous silicon composite negative pole material, main component is silicon, copper, carbon, the mass fraction of silicon is 30～99%, and the mass fraction of copper is 0.1～30%, and the mass fraction of carbon is 1～15%.
The present invention's industrial silicon waste material used derives from the organic silane process process of preparation or prepares the technical process of polysilicon presoma trichlorosilane, and wherein the molecular formula of organosilan is SiR
nx
4-n, n=1～3 in formula, X is Cl or Br, R is more than one groups in methyl, ethyl, propyl group, vinyl, phenyl.
In the preparation of porous silicon composite negative pole material of the present invention, organic substance carbon source used is more than one materials in glucose, fructose, sucrose, wood sugar, sorbose, ascorbic acid, starch, polyethylene, polypropylene, phenolic resins, furfural resin, polyacrylonitrile, cellulose, graphite, Graphene, aromatic hydrocarbon, aromatic series lipid.
Beneficial effect of the present invention: the chlorosilane that the every production of factory is 40,000 tons, by the siliceous industrial waste that produces 200 tons.The siliceous byproduct number of chlorosilane generation is prepared every year in power ton by China.Processing mode one is in the past landfill after recovery copper, not only causes huge waste, also can surrounding enviroment be produced and be polluted; The 2nd, filler or brickmaking using the silicon-carbon mixture after extraction copper as firecrackers, price is extremely cheap.The recycling approach of siliceous byproduct provided by the invention both can reduce the pollution to environment, can greatly improve again its added value of industry, can be used as the important ring in green energy resource industrial chain.The processing method of siliceous industrial waste of the present invention is simple, and auxiliary material cheapness has very strong industrial promotional value.The porous silicon composite material obtaining after the art of this patent is processed has good chemical property, as lithium ion battery negative material, has the specific capacity of 350～1600mAh/g.
Accompanying drawing explanation
Fig. 1 porous silicon composite material scanning electron microscopy (SEM) photo
Fig. 2 porous silicon composite material X-ray diffraction (XRD) collection of illustrative plates
Embodiment
Embodiment 1
Industrial silicon waste material is through pre-treatment step, after the sub-sorting of 500 mesh sieve, material joined in 30% sucrose solution, after fully stirring, obtains stable suspension-turbid liquid.By dry suspension-turbid liquid spraying, obtain the coated material of sucrose.Then 700 ℃ of heat treatment 16h, obtain silicon/copper/carbon composite.Mix with the ratio of 8: 1: 1 with acetylene black, Kynoar (PVDF) afterwards, add appropriate 1-METHYLPYRROLIDONE (NMP), be ground to modest viscosity, without granular sensation, be applied on Copper Foil.In baking oven, at 50 ℃, dry 8h, apply the pressure of 2MPa with hydraulic press.In vacuum drying oven, at 120 ℃, dry 10h afterwards, make pole piece, weigh.Pole piece thickness is 35～45 μ m.In glove box, take lithium sheet as negative pole, celgard2400 film is barrier film assembled battery, and electrolyte is 1M lithium hexafluoro phosphate (LiPF
6)/ethylene carbonate (EC)+dimethyl carbonate (DMC).At 0.2mA/cm
2under discharge and recharge, the reversible capacity of material reaches 870mAh/g.
Industrial silicon waste material is through pre-treatment step, and after the sub-sorting of 200 mesh sieve, drum's speed of rotation, at 100rpm ball milling 2h, adds 10% phenolic resins and appropriate ethanol, fully stirs spraying and is dried, and then 800 ℃ of heat treatment 16h, obtain silicon/copper/carbon composite.Mix with the ratio of 8: 1: 1 with acetylene black, PVDF afterwards, add appropriate NMP, be ground to modest viscosity, without granular sensation, be applied on Copper Foil.In baking oven, at 50 ℃, dry 8h, apply the pressure of 2MPa with hydraulic press.In vacuum drying oven, at 120 ℃, dry 10h afterwards, make pole piece, weigh.Pole piece thickness is 35～45 μ m.In glove box, take lithium sheet as negative pole, celgard2400 film is barrier film assembled battery, and electrolyte is 1MLiPF
6/ EC+DMC.At 0.2mA/cm
2under discharge and recharge, the reversible capacity of material reaches 550mAh/g.
Embodiment 3
Industrial silicon waste material, through pre-treatment step, after the sub-sorting of 200 mesh sieve, adds 30% ascorbic acid, and after grinding evenly, 800 ℃ of heat treatment 12h, obtain silicon/copper/carbon composite.Mix with the ratio of 8: 1: 1 with acetylene black, PVDF afterwards, add appropriate NMP, be ground to modest viscosity, without granular sensation, be applied on Copper Foil.In baking oven, at 50 ℃, dry 8h, apply the pressure of 2MPa with hydraulic press.In vacuum drying oven, at 120 ℃, dry 10h afterwards, make pole piece, weigh.Pole piece thickness is 35～45 μ m.In glove box, take lithium sheet as negative pole, celgard2400 film is barrier film assembled battery, and electrolyte is 1MLiPF
6/ EC+DMC.At 0.2mA/cm
2under discharge and recharge, the reversible capacity first of material reaches 1600mAh/g.
Embodiment 4
Siliceous industrial waste, adds in 0.1M watery hydrochloric acid, and stirring at normal temperature 0.5h filters, and is washed to without chloride ion.Detect through ICP, in product, Fe, Al ion concentration are below 10ppm.Products therefrom is carried out to ball milling, and drum's speed of rotation is at 100rpm, and Ball-milling Time is 2h, afterwards ball milling material is crossed to 500 mesh sieves.Products therefrom adds 20% phenolic resins, and 800 ℃ of heat treatment 16h, obtain silicon/copper/carbon composite.Composite material is prolonged in mortar broken, mix with the ratio of 8: 1: 1 with acetylene black, PVDF afterwards, add appropriate NMP, be ground to modest viscosity, without granular sensation, be applied on Copper Foil.In vacuum drying oven, at 120 ℃, dry 10h afterwards, make pole piece, weigh.Pole piece thickness is 35～45 μ m.In glove box, take lithium sheet as negative pole, celgard2400 film is the assembled battery of ball milling barrier film, and electrolyte is 1MLiPF
6/ EC+DMC.At 0.2mA/cm
2under discharge and recharge, the capacity first of material reaches 370mAh/g.
Claims (3)
1. prepare a method for lithium ion battery porous silicon composite negative pole material with industrial scrap silicon, this preparation method's step is as follows:
1. preliminary treatment: for the waste material of separate sources, use two kinds of preprocess methods, a kind of is that its pre-treatment step is 200～800 ℃ of pyrolysis silane polymers under nitrogen protection for the industrial silicon waste material that derives from preparation silane process process; Another kind is the industrial silicon waste material of preparing trichlorosilane technical process for deriving from, and its pre-treatment step is to clean with clear water, and cleaning method is immersion, extracting or stirring;
2. from preliminary treatment scrap silicon, sub-elect the particle that particle diameter is less than 1mm;
3. the material sub-electing is pulverized in ball milling or grinder to the micro mist that is less than 10 μ m for particle diameter;
4. take organic substance as carbon source, micropowder material is coated, organic mass percent example is 1%～40%;
5. in high temperature furnace, the micropowder material heat treated coated to carbon source, heat treatment temperature is 400～1000 ℃, heat treatment time is 0.1～72h, makes organic carbon and improves conductivity, obtains porous silicon composite negative pole material, main component is silicon, copper, carbon, the mass fraction of silicon is 30～99%, and the mass fraction of copper is 0.1～30%, and the mass fraction of carbon is 1～15%.
2. the industrial scrap silicon of use according to claim 1 is prepared the method for lithium ion battery porous silicon composite negative pole material, it is characterized in that described industrial silicon waste material derives from the technical process of preparing organic silane process process or preparing polysilicon presoma trichlorosilane, wherein the molecular formula of organosilan is SiR
nx
4-n, n=1～3 in formula, X is Cl or Br, R is more than one groups in methyl, ethyl, propyl group, vinyl, phenyl.
3. the industrial scrap silicon of use according to claim 1 is prepared the method for lithium ion battery porous silicon composite negative pole material, it is characterized in that as the organic substance of carbon source be more than one materials in glucose, fructose, sucrose, wood sugar, sorbose, ascorbic acid, starch, polyethylene, polypropylene, phenolic resins, furfural resin, polyacrylonitrile, cellulose, graphite, Graphene, aromatic hydrocarbon, aromatic series lipid.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105336922A (en) * | 2014-08-08 | 2016-02-17 | 苏州格瑞动力电源科技有限公司 | Preparation method and application for lithium ion battery negative electrode material based on photovoltaic silicon waste material |
| CN105789599A (en) * | 2016-02-02 | 2016-07-20 | 北京理工大学 | Method for preparing porous silicon cathode material by polyvinyl alcohol freezing-unfreezing crosslinked carbonization |
| CN105826528A (en) * | 2016-03-22 | 2016-08-03 | 浙江大学 | Porous silicon-copper composite material and preparation method and application thereof |
| CN109065873A (en) * | 2018-08-17 | 2018-12-21 | 东莞市凯金新能源科技股份有限公司 | A kind of preparation method and material of the mesoporous graphitic nitralloy carbon negative pole material of loaded nano-copper |
| CN109585834A (en) * | 2018-12-10 | 2019-04-05 | 包头市石墨烯材料研究院有限责任公司 | A kind of mesoporous silicon-tin composite electrode material and its preparation method and application |
| CN111153394A (en) * | 2020-01-16 | 2020-05-15 | 昆明理工大学 | Preparation method of carbon-silicon negative electrode material of lithium ion battery |
| CN115010137A (en) * | 2021-03-05 | 2022-09-06 | 中国科学院过程工程研究所 | Method for rapidly preparing silicon nanowires by using cut waste silicon powder and application |
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- 2012-12-10 CN CN201210526156.4A patent/CN103872296A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105336922A (en) * | 2014-08-08 | 2016-02-17 | 苏州格瑞动力电源科技有限公司 | Preparation method and application for lithium ion battery negative electrode material based on photovoltaic silicon waste material |
| CN105336922B (en) * | 2014-08-08 | 2018-09-07 | 江苏载驰科技股份有限公司 | A kind of preparation method and application of the lithium ion battery negative material based on photovoltaic scrap silicon |
| CN105789599A (en) * | 2016-02-02 | 2016-07-20 | 北京理工大学 | Method for preparing porous silicon cathode material by polyvinyl alcohol freezing-unfreezing crosslinked carbonization |
| CN105789599B (en) * | 2016-02-02 | 2018-05-08 | 北京理工大学 | The method that polyvinyl alcohol freeze-thaw cross-linking carbonization prepares porous silicon negative material |
| CN105826528A (en) * | 2016-03-22 | 2016-08-03 | 浙江大学 | Porous silicon-copper composite material and preparation method and application thereof |
| CN105826528B (en) * | 2016-03-22 | 2019-01-15 | 浙江大学 | A kind of porous silicon-carbon/carbon-copper composite material and its preparation method and application |
| CN109065873A (en) * | 2018-08-17 | 2018-12-21 | 东莞市凯金新能源科技股份有限公司 | A kind of preparation method and material of the mesoporous graphitic nitralloy carbon negative pole material of loaded nano-copper |
| CN109585834A (en) * | 2018-12-10 | 2019-04-05 | 包头市石墨烯材料研究院有限责任公司 | A kind of mesoporous silicon-tin composite electrode material and its preparation method and application |
| CN111153394A (en) * | 2020-01-16 | 2020-05-15 | 昆明理工大学 | Preparation method of carbon-silicon negative electrode material of lithium ion battery |
| CN111153394B (en) * | 2020-01-16 | 2023-01-20 | 昆明理工大学 | Preparation method of carbon-silicon negative electrode material of lithium ion battery |
| CN115010137A (en) * | 2021-03-05 | 2022-09-06 | 中国科学院过程工程研究所 | Method for rapidly preparing silicon nanowires by using cut waste silicon powder and application |
| CN115010137B (en) * | 2021-03-05 | 2023-12-19 | 中国科学院过程工程研究所 | Method for rapidly preparing silicon nanowires by using cut waste silicon powder and application |
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Application publication date: 20140618 |