CN104701491A - Nano-porous silica lithium battery anode material and preparation method and application thereof - Google Patents
Nano-porous silica lithium battery anode material and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention provides a nano-porous silica lithium battery anode material and a preparation method and an application thereof. The preparation method of the nano-porous silica lithium battery anode material comprises the steps that 1, silica powder waste generated in a silica wafer production process is filtered, settled, acid pickled, cleaned and dried, so that silica powder is obtained, or metallic silica powder with the purity being higher than 99% and the average grain diameter being 1 micro to 6 micros is directly selected; 2, dyeing and chemical corrosion are conducted on the silica powder, so that nano-porous silica powder is obtained; 3, fluorescence detection is conducted on the nano-porous silica powder; 4, the nano-porous silica powder, a conductive agent and an adhesion agent are mixed according to a certain ratio to be made into slurry, a metal collector is coated with the slurry, and then the nano-porous silica lithium battery anode material is obtained. The nano-porous silica lithium battery anode material is high in porosity and capable of resisting to volume expansion generated in the lithium insertion and removal process on a lithium battery, the silicone powder generated in the silicon wafer process is effectively recycled, and environmental pollution is reduced.
Description
Technical field
The present invention relates to a kind of lithium cell cathode material and preparation method thereof and application, especially relate to a kind of preparation method and application of nano-structure porous silicon lithium cell cathode material.
Background technology
Silicon is that the industrial output of modern semiconductors is maximum, most widely used a kind of material.The main process that silicon chip is produced is by crystal growth, and the machining steps such as crystal-cut have been come.Such as photovoltaic industry monocrystalline silicon piece, the production process of polysilicon chip, the steps such as mainly silicon ingot evolution, blocks, edging, Linear cut form.
Along with the develop rapidly of photovoltaic industry, the consumption of silicon materials sharply expands, and has exceeded the consumption of semiconductor applications at present, and the consumption of domestic self-produced high purity polycrystalline silicons in 2014 and import polysilicon reaches about 220,000 tons.
The cutting of silicon chip, grind, process that throwing process is a mechanical grinding, the multi-wire saw process of such as silicon chip, mean under the drive of line of cut, cut tough confrontation silicon crystal to clash into, the silicon area cut between adjacent line is silicon chip, thus is then knocked along the silicon of line of cut cut direction, and fragmentation becomes tiny micro mist, cooled liquid is taken away, and becomes the primary solids composition of the rear waste slurry of cutting.In whole machining process from silicon crystal to silicon chip, the silicon materials of nearly about 40-50% have been wasted with the form of micro mist, and the particle diameter of these silicon powders is minimum, average grain diameter at about 2-3 μm, very close to nanoscale.According to statistics, whole nation silicon wafer to manufacture enterprise about produces the useless silicon powder of 8-10 about ten thousand tons every year, process if inappropriate, these micro mists will form dust, contaminated environment and human health, but these silicon powders cut down from high quality silicon crystal, have very high purity and quality, how to be re-used by these useless silicon powders, be a difficult problem of puzzlement silicon chip industry always.
Nano-structure porous silicon, also referred to as sponge silicon, as the term suggests be a kind of material silicon nanoparticle having many holes, he is the silicon materials that a kind of porosity is very high.Because its porosity is high, therefore there is the feature being much different from traditional silicon material, as fluoresced, chemism, anti-volumetric expansion etc., through for many years to the research of nano-structure porous silicon, its preparation method is also more and more diversified, the method studied now mainly contains the preparation of porous silicon method, prepared by reactive ion etching, the several methods such as the preparation of femto-second laser irradiation and metal assistant chemical etch.These methods are all surfaces porous silicon reflector being prepared in silicon chip, and required equipment mainly laser, ion device etc.No matter be with femtosecond laser processing, or etch by ion device, or the method for porous silicon corrosion, all need to use special equipment, such as vacuum equipment or powerful laser aid, have high input, operating cost is high.
Along with various countries are to the pay attention to day by day of environmental protection; new-energy automobile particularly Development of Electric Vehicles enters the blowout phase; the electrokinetic cell lithium battery supporting as key receives increasing concern, and the new material being especially applicable to lithium-ion-power cell also will enter a develop rapidly phase.
At present, the lithium cell cathode material mainly carbon class material that business uses, as graphite, carbosphere etc., but the capacity of Carbon anode oneself through closely its theoretical capacity (372 mAh/g), the potentiality to be exploited of specific capacity is little, and has certain potential safety hazard when over-charging of battery, and therefore the research negative material of sending out of new generation height ratio capacity and high security is just particularly urgent.
Although silicon has the specific capacity up to 4200mAh/g, look like the negative material of desirable height ratio capacity and safety, but silicon takes off in lithium process the change in volume having 320% at embedding lithium, this often causes the efflorescence of silicon active material, and comes off from the collector electrode of coating, loses charge-discharge characteristic.In addition, silicon is a kind of intrinsic material, and do not carry out adulterating or coating modification, its conductivity is poor more than material with carbon elements such as graphite, therefore, can not form effective conductive network, realizes effectively discharge and recharge rapidly.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the above-mentioned defect that prior art exists, and provides one to take off change in volume in lithium process at embedding lithium little, not easily efflorescence, nano-structure porous silicon lithium cell cathode material of charge-discharge performance excellence and preparation method thereof.
The technical problem that the present invention will solve further is, provides a kind of and applies the method that described nano-structure porous silicon lithium cell cathode material manufactures lithium battery.
The technical scheme that the present invention solves the employing of its technical problem is that a kind of nano-structure porous silicon lithium cell cathode material, is prepared from by the following method:
(1) the waste slurry filtering-depositing will produced in silicon chip production process, pickling impurity removal (pickling impurity removal, watery hydrochloric acid or HF acid soak 1-10h that usable concentration is less than 10%), and dry, obtain silicon powder, or directly to choose purity be more than 99%, average grain diameter (D50) is the metallic silicon micro mist of 1 ~ 6 μm, carry out further ball-milling treatment, Ball-milling Time is 4-10 hour;
Ball milling, should select the Ceramic Balls of high strength, and ratio of grinding media to material is preferably the preferred 3:1 of 2-4:1();
(2) silicon powder after step (1) ball-milling treatment is placed in the strong acid for stain etch, corrode, etching time is 5 ~ 180 minutes (preferably 10 ~ 90 minutes), or there is khaki porous silicon foam, or no longer to produce bubble in solution; The strong acid of described stain etch is by HF, HNO
3and H
2o forms, wherein HF:HNO
3: H
2the mol ratio of O is 20 ~ 1:1:20 ~ 10;
Described nitric acid mainly plays the oxidation to silica flour, and HF works the oxide corroding silicon; First be oxidized by nitric acid by silica flour, then HF corrodes the method for the oxide of silicon again, forms the nano-porous structure of silicon.
In course of reaction, bubble can be observed and produce, and part is yellow or filemot porous silicon due to hydrophobic property floating to liquid level.
Described nitric acid can the replacement such as some or all of nitrate, nitrite, potassium permanganate, potassium chromate or Potassiumiodate.Described nitrate can be Fe (NO
3)
3or AgNO
3, described nitrite can be NaNO
2.
(3) silicon powder after step (2) process is carried out suction filtration, dry, and carry out fluoroscopic examination, namely irradiate with the laser of ultraviolet or visible light source, if there is reddish yellow fluorescence to produce, then corrosive effect reaches, and obtains nanoporous silica flour; Otherwise, proceed step (2);
Through stain etch, the particle diameter of nano-structure porous silicon, at about 600-800nm, should select filter opening at 220nm, the filter membrane of hf resi stant can carry out suction filtration; The main material of suction filtration container is Tai Fulong plastics;
(4) be 8 ~ 7:1 ~ 2:1 in mass ratio by nano-structure porous silicon and conductive agent, binding agent after step (3) process, employing 1-METHYLPYRROLIDONE (NMP) or water make solvent, are mixed with form slurry;
Described conductive agent is flaky graphite powder or conductive black, and described binding agent is Kynoar (PVDF), sodium alginate or sodium carboxymethylcellulose (when binding agent is Kynoar, make solvent with 1-METHYLPYRROLIDONE; When binding agent be sodium alginate or sodium carboxymethylcellulose time, make solvent with water);
(5) be coated in metal collector by the slurry after step (4) process, the coating thickness of coating is 80-120 μm (preferably 100 μm), and be placed in convection oven and dry, bake out temperature is 80-100 DEG C, and drying time is 1-4h;
(6) the metal collector roll squeezer after step (5) process is carried out roll-in, make coating layer thickness be 60-80 μm, obtain the negative material of nano-structure porous silicon lithium battery.
Further, in preparation method's step (1), the waste slurry produced in described silicon chip production process for from the useless silicon material produced in diamond wire in silicon chip production technology or multi-wire saw process, or polishing, polishing, block the waste silicon powder produced in silico briquette machining process.
Further, in preparation method's step (2), silicon powder is preferably mixed to form solution with HF in advance, then by HNO
3or nitrate or nitrite join in solution.This is conducive to controlling the directional etching to silicon powder, forms nano-structure porous silicon.
Further, in preparation method's step (4), in order to improve the conductivity of nano-structure porous silicon, can with mesophase pitch and the nano-structure porous silicon Homogeneous phase mixing being equivalent to nano-structure porous silicon weight 1-5%, then 1000-1200 DEG C is warming up to 5-8 DEG C/min, lower the temperature after constant temperature 1-2 hour, bituminous texture, from recombinating and being formed porous silicon coated, forms effective conductive network.
Further, in preparation method's step (4), in order to improve the conductivity of nano-structure porous silicon, the carbon nano-tube being equivalent to conductive agent weight 2-5% can also be added in conductive agent, to utilize the Micro-scale length of carbon nano-tube, optimizing conductive network.
The nano-structure porous silicon lithium cell cathode material of the present invention, can be used for making various types of cathode of lithium battery.
The nano-structure porous silicon lithium cell cathode material of the present invention, for the manufacture of button lithium battery, can adopt following methods:
(1) described nano-structure porous silicon lithium cell cathode material being prepared into diameter is 1.4cm circular electric pole piece;
(2) adopt metal lithium sheet as positive pole, select poly-two rare micro-pore septums (Celgard2300), adopt 1M LiPF
6cruel (the DEC)+methyl ethyl carbonate of the rare ester of/ethylene (EC)+carbonic acid diethyl cruel (EMC), the wherein rare ester of ethylene, carbonic acid diethyl is cruel, methyl ethyl carbonate is cruel volume ratio=1:1:1, as electrolyte, the circular electric pole piece after step (1) process being made negative pole in glove box, be assembled into CR2032 button cell.
The present invention adopts from the cutting of silicon chip diamond wire or polishing, the silicon powder waste slurry that produces bruting process, and after being purified to required purity by pickling, then carrying out dyeing strong acid and corrode, the silicon powder be prepared into has nanoporous, the features such as anti-volumetric expansion.Nanoporous silica flour can according to the electric conductivity of silica flour self, with the conductive agent of different proportion, (preferred mixed ratio is, nano-structure porous silicon: conductive agent: binding agent 8 ~ 7:1 ~ 2:1 in binding agent mixing, coordinate positive electrode etc., make circular lithium battery or quadrate lithium battery.
Because nano-structure porous silicon contained in material of the present invention is micro mist shape, similar to the negative material graphite powder pattern of existing lithium battery, therefore their lithium battery preparation manipulation step and equipment can be compatible.
A kind of method of simple controlled chemical corrosion of the present invention, the silicon powder waste material in being produced by photovoltaic, is transformed into the negative material of the very high nano-structure porous silicon lithium battery of value.
The present invention processes the useless silicon powder produced in silicon chip production process, form nanoporous silicon materials, by the pore structure of porous silicon self, because the impact of volumetric expansion and powder of detached when effective elimination takes off lithium as the embedding lithium of cathode of lithium battery, simultaneously also because silicon chip itself has had conductive doped property, the nano-structure porous silicon of corresponding useless silicon powder and preparation has certain conductive doped property, thus can take off in lithium process at embedding lithium and form effective conductive network, improves chemical property.
Compared with prior art, the present invention has the following advantages:
(1) nano-structure porous silicon has larger porosity (porosity > 70%), can resist embedding lithium in lithium battery and take off the volumetric expansion produced in lithium process, therefore, be used to the ideal material doing cathode of lithium battery.
(2) raw material of the present invention is the useless silicon material from producing in silicon chip production process, mainly silicon slurry in silicon chip Linear cut process, silicon rod, silicon ingot polishing, polishing, the useless micro mist produced in truncated process, and twice laid, turns waste into wealth; Meanwhile, this silicon powder has certain conductivity due to silicon chip doping, after being prepared into nano-structure porous silicon, and the characteristic that can be improved charging and discharging lithium battery speed.
(3) adopt controlled stain etch legal system for nano-structure porous silicon lithium cell cathode material, equipment needed thereby and technique are relatively simple, and the silicon raw material in addition used is the useless silicon material produced in silicon chip production process, and therefore, production cost is low, are suitable for producing in enormous quantities.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The preparation method of the nano-structure porous silicon lithium cell cathode material of the present embodiment, comprises the following steps:
(1) the waste slurry filtering-depositing will produced in multi-wire saw process in silicon chip production technology, pickling impurity removal (soaking 5h with the watery hydrochloric acid of mass concentration 8%), dry, obtain silicon powder, also containing a small amount of tough matter carborundum of cutting in this silicon powder, choose from silicon powder average grain diameter about 1 μm carry out further ball-milling treatment; Ball milling adopts the Ceramic Balls of high strength, and ratio of grinding media to material is 3:1, and Ball-milling Time is 4 hours;
(2) silicon powder after step (1) ball-milling treatment is placed in strong acid, carries out strong acid corrosion, etching time is 60 minutes, and described strong acid is by HF, HNO
3and H
2o forms; HF:HNO
3: H
2the mol ratio of O is 20:1:20; Along with the aggravation of reaction, constantly have hydrophobic khaki nano-silicon floatation of foam to liquid level, adopt container collection these foams, while carborundum impurity do not react, be deposited at the bottom of liquid gradually, thus automatically achieve being separated of impurity and nano-silicon.
(3) silicon powder after step (2) process is carried out suction filtration, dry, and carry out fluoroscopic examination, namely use the laser of ultraviolet (or visible ray) light source to irradiate, until there is reddish yellow fluorescence to produce, obtain nanoporous silica flour; Detect and learn that the mean porosities of nanoporous silica flour is 78%;
(4) be that 7:2:1 mix with conductive agent, binding agent according to mass ratio by the nano-structure porous silicon after step (3) process, employing 1-METHYLPYRROLIDONE makees solvent, is mixed with form slurry; Described conductive agent is conductive black, and described binding agent is Kynoar (PVDF);
(5) be coated on Copper Foil by the slurry after step (4) process, the coating thickness of coating is 100 μm, is placed in convection oven and dries, and bake out temperature is 80 DEG C, drying time 4h;
(6) by through step (5) process after Copper Foil through roll squeezer pressure, make coating layer thickness be 70 μm, obtain the negative material of nano-structure porous silicon lithium battery.
Application: it is 1.4cm circular electric pole piece that the negative material of nano-structure porous silicon lithium battery is prepared into diameter by (1); (2) adopt metal lithium sheet as positive pole, select poly-two rare micro-pore septums (Celgard2300), adopt 1M LiPF
6cruel (EMC) (volume ratio=1:1:1) of cruel (the DEC)+methyl ethyl carbonate of the rare ester of/ethylene (EC)+carbonic acid diethyl as electrolyte, in glove box will after step (1) process circular electric pole piece be assembled into CR2032 button cell.
With traditional lithium battery (graphite cathode material, specific capacity is 372 mAh/g) compare, the nano-structure porous silicon lithium battery of the present invention's encapsulation adopts specific capacity and the cycle performance of galvanostatic charge/discharge test material, testing inspection result is the specific capacity first of negative material is 900mAh/g, it is 2.4 times of graphite cathode material specific capacity, remain on 856mAh/g after 100 circulations, decay to 5%.
Embodiment 2
The difference of the present embodiment and embodiment 1 is only: in step (1), silicon powder to be purity be 99% metallic silicon micro mist, choose average grain diameter about 2 μm carry out further ball-milling treatment; Ball milling adopts the Ceramic Balls of high strength, and ratio of grinding media to material is 3:1, and Ball-milling Time is 10 hours; Step (2) strong acid HF:HNO
3: H
2molar ratio=the 4:1:10 of O; The oxidant NaNO of 2% is added in strong acid
2, etching time is 5 minutes; Detect in step (3) and learn that the mean porosities of nanoporous silica flour is 80%; Step (4) nano-structure porous silicon and conductive agent, binding agent are 8:1:1 according to mass ratio, adopt deionized water to make solvent, are mixed with form slurry; Described conductive agent is flaky graphite powder, and described binding agent is sodium alginate; Step (5) bake out temperature is 90 DEG C, and drying time is 2h; Step (6) coating layer thickness is 80 μm.
With traditional lithium battery (graphite cathode material, specific capacity is 372 mAh/g) compare, the nano-structure porous silicon lithium battery of the present invention's encapsulation adopts specific capacity and the cycle performance of galvanostatic charge/discharge test material, testing inspection result is the specific capacity of negative material is 1100mAh/g, it is nearly 3 times of graphite cathode material specific capacity, after 100 circulations, specific capacity remains on 1020mAh/g, decays to 8%.
Embodiment 3
The difference of the present embodiment and embodiment 1 is only: step (1), waste slurry is for from the useless silicon material produced in diamond wire cutting process in silicon chip production technology, silicon powder choose average grain diameter 6 μm carry out further ball-milling treatment, ball milling adopts the Ceramic Balls of high strength, ratio of grinding media to material is 3:1, and Ball-milling Time is 9 hours; Step (2) strong acid HF:HNO
3: H
2molar ratio=the 1:1:10 of O; Etching time is 180 minutes; Detect in step (3) and learn that the mean porosities of nanoporous silica flour is 81%; Step (4) nano-structure porous silicon and conductive agent, binding agent are 8:2:1 according to mass ratio, adopt 1-METHYLPYRROLIDONE (NMP) to make solvent, are mixed with form slurry, add the carbon nano-tube of 4% quality in conductive black; Step (5) bake out temperature is 100 DEG C, and drying time is 1h; Step (6) coating layer thickness is 60 μm.
With traditional lithium battery (graphite cathode material, specific capacity is 372 mAh/g) compare, the nano-structure porous silicon lithium battery of the present invention's encapsulation adopts specific capacity and the cycle performance of galvanostatic charge/discharge test material, testing inspection result is the specific capacity of negative material is 1150mAh/g, it is 3 times of graphite cathode material specific capacity, after 100 circulations, specific capacity remains on 980mAh/g, decays to 15%.
Embodiment 4
The difference of the present embodiment and embodiment 1 is only: step (1) waste slurry is for from the useless silicon material produced in multi-wire saw process in silicon chip production technology, silicon powder choose average grain diameter about 3 μm carry out further ball-milling treatment, ball milling adopts the Ceramic Balls of high strength, ratio of grinding media to material is about 3:1, and Ball-milling Time is 7 hours; Step (2) strong acid is HF and Fe (NO
3)
3mixture, HF:Fe (NO
3)
3: H
2mol ratio=the 12:1:18 of O, etching time: to occurring khaki porous silicon foam (about 20 minutes); Detect in step (3) and learn that the mean porosities of nanoporous silica flour is 83%; Step (4) nano-structure porous silicon and conductive agent, binding agent are 7.5:1.5:1 according to mass ratio, adopt deionized water to make solvent, are mixed with form slurry, add the carbon nano-tube of 5% quality in conductive black; Described binding agent is sodium carboxymethylcellulose; Step (5) bake out temperature is 90 DEG C, and drying time is 2h; Step (6) coating layer thickness is 80 μm.
With traditional lithium battery (graphite cathode material, specific capacity is 372 mAh/g) compare, the nano-structure porous silicon lithium battery of the present invention's encapsulation adopts specific capacity and the cycle performance of galvanostatic charge/discharge test material, testing inspection result is the specific capacity of negative material is 1200mAh/g, it is about 3.2 times of graphite cathode material specific capacity, after 100 circulations, specific capacity still remains on 1060mAh/g, decays to 12%.
Embodiment 5
The difference of the present embodiment and embodiment 1 is only: step (1) waste slurry is for from the useless silicon material produced in polishing process in silicon chip production technology, silicon powder choose average grain diameter 2 μm carry out further ball-milling treatment, ball milling adopts the Ceramic Balls of high strength, ratio of grinding media to material is 3:1, and Ball-milling Time is 5 hours; Step (2) strong acid is HF and HNO
3mixture, HF:HNO
3: H
2molar ratio=the 5:1:10 of O, etching time is 90 minutes; Detect in step (3) and learn that the mean porosities of nanoporous silica flour is 76%; The carbon nano-tube of 2% quality is added in step (4) conductive black; Step (5) bake out temperature is 85 DEG C, and drying time is 3h; Step (6) coating layer thickness is 75 μm.
With traditional lithium battery (graphite cathode material, specific capacity is 372 mAh/g) compare, the nano-structure porous silicon lithium battery of the present invention's encapsulation adopts specific capacity and the cycle performance of galvanostatic charge/discharge test material, testing inspection result is the specific capacity of negative material is 1210mAh/g, it is 3.2 times of graphite specific capacity, after 100 circulations, still remain on 1150mAh/g, decay 5%.
Embodiment 6
The difference of the present embodiment and embodiment 1 is only: step (1) waste slurry is for from the useless silicon material produced in bruting process in silicon chip production technology, silicon powder choose average grain diameter about 4 μm carry out further milled processed, ball milling adopts the Ceramic Balls of high strength, ratio of grinding media to material is about 3:1, and Ball-milling Time is 8 hours; Step (2) strong acid is the mixture of HF and potassium permanganate, HF: potassium permanganate: H
2mol ratio=the 2:1:12 of O, adds appropriate AgNO in strong acid
3, etching time is 10 minutes; Detect in step (3) and learn that the mean porosities of nanoporous silica flour is 78%; After the mesophase pitch Homogeneous phase mixing of step (4) nano-structure porous silicon and 1% weight ratio, be warming up to 1000 DEG C with 5 DEG C/min, constant temperature was lowered the temperature after 2 hours, and bituminous texture is from recombinating and being formed nano-structure porous silicon coated; Step (5) bake out temperature is 85 DEG C, and drying time is 3h; Step (6) coating layer thickness is 75 μm.
With traditional lithium battery (graphite cathode material, specific capacity is 372 mAh/g) compare, the nano-structure porous silicon lithium battery of the present invention's encapsulation is through the specific capacity of galvanostatic charge/discharge test material and cycle performance, testing inspection result is the specific capacity of negative material is 1180mAh/g, it is about 3.1 times of graphite specific capacity, after 100 circulations, specific capacity remains on 995mAh/g, and decay is about 16%.
Embodiment 7
The difference of the present embodiment and embodiment 1 is only: step (1) waste slurry is from blocking the waste silicon powder produced in silico briquette machining process in silicon chip production technology, silicon powder choose average grain diameter about 3 μm carry out further ball-milling treatment, ball milling adopts the Ceramic Balls of high strength, ratio of grinding media to material is about 3:1, and Ball-milling Time is 6 hours; Step (2) strong acid is the mixture of HF and potassium chromate, HF: potassium chromate: H
2mol ratio=the 15:1:15 of O, etching time: to occurring khaki porous silicon foam; Detect in step (3) and learn that the mean porosities of nanoporous silica flour is 79%; After the mesophase pitch Homogeneous phase mixing of step (4) nano-structure porous silicon and 5% weight ratio, be warming up to 1200 DEG C with 8 DEG C/min, constant temperature was lowered the temperature after 1 hour, and bituminous texture is from recombinating and being formed nano-structure porous silicon coated; Step (5) bake out temperature is 90 DEG C, and drying time is 2h; Step (6) coating layer thickness is 80 μm.
With traditional lithium battery (graphite cathode material, specific capacity is 372 mAh/g) compare, the nano-structure porous silicon lithium battery of the present invention's encapsulation is through the specific capacity of galvanostatic charge/discharge test material and cycle performance, testing inspection result is the specific capacity of negative material is 1220mAh/g, it is about 3.3 times of graphite cathode material specific capacity, after 100 charge and discharge cycles, specific capacity is at 1180mAh/g, does not substantially decay.
Embodiment 8
The difference of the present embodiment and embodiment 1 is only: step (1) waste slurry is from blocking the waste silicon powder produced in silico briquette machining process in silicon chip production technology, silicon powder choose average grain diameter 4 μm carry out further ball-milling treatment, ball milling adopts the Ceramic Balls of high strength, ratio of grinding media to material is 3:1, and Ball-milling Time is 8 hours; Step (2) strong acid is the mixture of HF and Potassiumiodate, HF: Potassiumiodate: H
2mol ratio=the 16:1:114 of O, etching time is 120 minutes; Detect in step (3) and learn that the mean porosities of nanoporous silica flour is 85%; After the mesophase pitch Homogeneous phase mixing of step (4) nano-structure porous silicon and 3% weight ratio, be warming up to 1150 DEG C with 7 DEG C/min, constant temperature was lowered the temperature after 1.5 hours, and bituminous texture is from recombinating and being formed nano-structure porous silicon coated; Step (5) bake out temperature is 88 DEG C, and drying time is 3h; Step (6) coating layer thickness is 65 μm.
With traditional lithium battery (graphite cathode material, specific capacity is 372 mAh/g) compare, the nano-structure porous silicon lithium battery of the present invention's encapsulation is through the specific capacity of galvanostatic charge/discharge test material and cycle performance, testing inspection result is the specific capacity of negative material is 1225mAh/g, it is about 3.3 times of graphite cathode material specific capacity, after 100 circulations, its specific capacity is 1165mAh/g, and decay is about 5%.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention, every above embodiment is done according to the technology of the present invention essence any amendment, change and equivalent structure transformation, all still belong to the protection range of technical solution of the present invention.
Claims (10)
1. a nano-structure porous silicon lithium cell cathode material, is characterized in that, is prepared from by the following method:
(1) the waste slurry filtering-depositing will produced in silicon chip production process, pickling impurity removal, and dry, obtain silicon powder, or directly to choose purity be more than 99%, average grain diameter is the metallic silicon micro mist of 1 ~ 6 μm, carry out further ball-milling treatment, Ball-milling Time is 4-10 hour;
(2) silicon powder after step (1) ball-milling treatment is placed in the strong acid solution for stain etch, corrodes, etching time is 5 ~ 180 minutes, until there is khaki porous silicon foam, or no longer produces bubble in solution; The strong acid solution of described stain etch is by HF, HNO
3and H
2o forms, wherein HF:HNO
3: H
2the mol ratio of O is 20 ~ 1:1:20 ~ 5;
(3) silicon powder after step (2) process is carried out suction filtration, dry, and carry out fluoroscopic examination, namely irradiate with the laser of ultraviolet or visible light source, if there is reddish yellow fluorescence to produce, then corrosive effect reaches, and obtains nanoporous silica flour; Otherwise, proceed step (2);
(4) be 8 ~ 7:1 ~ 2:1 in mass ratio by the nano-structure porous silicon after step (3) process and conductive agent, binding agent, according to the characteristic of binding agent, select 1-METHYLPYRROLIDONE or water to make solvent, be mixed with form slurry;
Described conductive agent is flaky graphite powder or conductive black, and described binding agent is Kynoar, sodium alginate or sodium carboxymethylcellulose;
(5) be coated in metal collector by the slurry after step (4) process, the coating thickness of coating is 80 ~ 120 μm, is placed in convection oven and dries, and bake out temperature is 80-100 DEG C, and drying time is 1-4h;
(6) by through step (5) process after metal collector through roll squeezer roll-in, make coating layer thickness be 60-80 μm, obtain the negative material of nano-structure porous silicon lithium battery.
2. nano-structure porous silicon lithium cell cathode material as claimed in claim 1, it is characterized in that, in preparation method's step (1), the waste slurry produced in described silicon chip production process is for from the useless silicon material produced in diamond wire in silicon chip production technology or multi-wire saw process, or polishing, polishing, block the waste silicon powder produced in silico briquette machining process.
3. nano-structure porous silicon lithium cell cathode material as claimed in claim 1, it is characterized in that, in preparation method's step (2), silicon powder is mixed to form solution with HF in advance, then by HNO
3join in solution.
4. the nano-structure porous silicon lithium cell cathode material as described in claim 1 or 2 or 3, it is characterized in that, in preparation method's step (4), with the mesophase pitch and the nano-structure porous silicon Homogeneous phase mixing that are equivalent to nano-structure porous silicon weight 1-5%, then 1000-1200 DEG C is warming up to 5-8 DEG C/min, lower the temperature after constant temperature 1-2 hour, bituminous texture, from recombinating and being formed porous silicon coated, forms conductive network.
5. the nano-structure porous silicon lithium cell cathode material as described in claim 1 or 2 or 3, it is characterized in that, in preparation method's step (4), in conductive agent, add the carbon nano-tube being equivalent to conductive agent weight 2-5%, utilize the Micro-scale length of carbon nano-tube, optimize conductive network.
6. nano-structure porous silicon lithium cell cathode material as claimed in claim 4, is characterized in that, in preparation method's step (4), add the carbon nano-tube being equivalent to conductive agent weight 2-5% in conductive agent, utilize the Micro-scale length of carbon nano-tube, optimizes conductive network.
7. the nano-structure porous silicon lithium cell cathode material as described in claim 1 or 2 or 3, is characterized in that, in preparation method's step (4), and described HNO
3some or all of nitrate, nitrite, potassium permanganate, potassium chromate or Potassiumiodate are replaced.
8. nano-structure porous silicon lithium cell cathode material as claimed in claim 7, it is characterized in that, described nitrate is Fe (NO
3)
3or AgNO
3, described nitrite is NaNO
2.
9. the nano-structure porous silicon lithium cell cathode material as described in one of claim 1-8 is preparing the application in lithium battery.
10. nano-structure porous silicon lithium cell cathode material as claimed in claim 9 is preparing the application in lithium battery, it is characterized in that, comprises the following steps:
(1) described nano-structure porous silicon lithium cell cathode material being prepared into diameter is 1.4cm circular electric pole piece;
(2) adopt metal lithium sheet as positive pole, select poly-two rare micro-pore septums (Celgard2300), adopt 1M LiPF
6/ ethylene rare ester+carbonic acid diethyl is cruel+and methyl ethyl carbonate is cruel, wherein volume ratio=the 1:1:1 of the rare ester of ethylene, carbonic acid diethyl is cruel, methyl ethyl carbonate is cruel volume ratio=1:1:1, make electrolyte, the circular electric pole piece after step (1) process being made negative pole in glove box, be assembled into CR2032 button cell.
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