CN106941153A - Flocculence elemental silicon nanowire cluster/carbon compound cathode materials and preparation method and purposes - Google Patents
Flocculence elemental silicon nanowire cluster/carbon compound cathode materials and preparation method and purposes Download PDFInfo
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Abstract
Present invention design battery material technical field, it is related to flocculence elemental silicon nanowire cluster/carbon compound cathode materials and preparation method and purposes, flocculence elemental silicon nanowire cluster/carbon compound cathode materials, described elemental silicon nanowire cluster is the flocculence structure being combined into simple substance silicon nanowires or/and simple substance nano silicon particles, at least a kind of conductive material in conductive carbon material or hybrid conductive material formation lithium ion battery negative material, described hybrid conductive material is coated with the outer surface and its space of elemental silicon nanowire cluster；Preparation method is prepared polymer solution, polymer solution is uniformly mixed with flocculence elemental silicon nanowire cluster, flocculence elemental silicon nanowire cluster/carbon compound cathode materials are obtained through filtering drying, carbonization, crushing, sieving again, for the GND of lithium battery, advantage is：Production is pollution-free, has the internal stresses release space of blast protection, silicon grain can be avoided directly to be contacted with electrolyte, slows down capacity attenuation speed, improves first charge-discharge efficiency, charge/discharge capacity and cycle performance.
Description
Technical field
Present invention design battery material technical field, and in particular to a kind of high power capacity, the good flocculence of long circulating stability
Elemental silicon nanowire cluster/carbon compound cathode materials and its production and use.
Background technology
Rapid expansion and rapid development of economy with population, using lithium ion battery as the electrochemistry of main forms
Energy storage is environment-friendly with its, has extended cycle life, and self discharge is small, and energy density is high and of great interest and green grass or young crops the features such as high voltage
Look at, be used widely in all kinds of portable type electronic products, but by existing graphite cathode material energy storage mechanism and low
The influence of capacity, current commercial li-ion battery is difficult to meet the use need to high-energy-density such as new-energy automobile power battery
Ask, elemental silicon is well-known theory capacity highest negative material (4200mAh/g), this is higher than commercial graphite cathode (372mAh/
g).There are more rich earth's crust reserves simultaneously, with suitable operating voltage, it is considered to be most potential high power capacity negative pole material
Material selection first of material.
However, silicon is as semi-conducting material, the conducting power to lithium ion and electronics is poor, and silicon and lithium alloyage reaction are led
Cause particle volume expansion in charge and discharge process to be up to 0-300%, easily cause electrode structure to destroy, battery capacity decay is violent,
Problem above seriously limits silicon and used as the scale of negative material, by silicon grain be reduced to nanosizing size Control in
Below 100nm.Silicon grain is because with the cubical expansivity that silicon is greatly reduced after particle nanosizing, and 60nm nano-silicon expansion rates are about
0-55% to reduce electrode interior stress, and with conductive carbon material is compound has been demonstrated that its chemical property can be effectively improved,
It is the main flow direction that current high power capacity high performance silicon negative material research institute takes.
It is main with chemical reactions such as silicon monoxide, silica, tetrachloro hydrogen silicon, the sub- silicon of oxidation that prior art prepares nano-silicon
Also original preparing nano level (100nm) following nano-silicon, its used device is huge, and big for environment pollution, its laboratory is small
Amount trial-production is feasible, but brings many technical bottleneck problems to industrialized mass production, and industrial mass can not be carried out at all
Amount production.
Global new-energy automobile present situation is to carry out that car is looked forward to subsidize by national governments, and new energy is developed using encouragement policy
Automobile, but long-term subsidized by government finance is infeasible.Solve the fast development of new-energy automobile it may first have to solve
The energy density of automobile power cell is improved, and improves course continuation mileage, ordinary people is bought new-energy automobile and is feared once to fill
Electricity can not travel long range distance and be addressed, and could solve the real marketization fast development of new-energy automobile, China could be true
Turn into new-energy automobile manufacturing power in positive meaning.
The China Patent Publication No. of prior art before the present invention is as follows：(Chinese science technology is big by CN106058207A
Learn), CN106252622A (Bei Terui), CN104466185A (Shenzhen Institutes of Advanced Technology, Chinese Academy of Science),
CN104362311A (Shenzhen research institute of Tsing-Hua University), CN102509781A (Shanghai Communications University), CN103545493A are (Central-South
University), CN10331522A (Chinese Academy Of Sciences Process Engineering Research Institute), (Chinese Academy of Sciences's Ningbo material is ground CN102790204A
Study carefully institute).
The content of the invention
It is an object of the invention to provide a kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials and preparation method and
Purposes.
The object of the present invention is achieved like this：
A kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials, described elemental silicon nanowire cluster is to use simple substance
Be coated with the flocculence structure that silicon nanowires is combined into, the outer surface and its space of elemental silicon nanowire cluster conductive carbon material or
At least a kind of conductive material in hybrid conductive material formation lithium ion battery negative material, described hybrid conductive material.
Above-mentioned elemental silicon nanowire cluster is the flocculence structure being combined into simple substance nano silicon particles, simple substance silicon nanowires
Conductive carbon material or hybrid conductive material formation lithium ion battery negative material are coated with the outer surface and its space of group, it is described
Hybrid conductive material at least a kind of conductive material.
Above-mentioned elemental silicon nanowire cluster is the flocculence knot being combined into simple substance nano silicon particles and simple substance silicon nanowires
Conductive carbon material or hybrid conductive material formation lithium-ion electric are coated with structure, the outer surface and its space of elemental silicon nanowire cluster
At least a kind of conductive material in pond negative material, described hybrid conductive material.
In above-mentioned elemental silicon nanowire cluster structure, the quality of a diameter of 15nm-300nm simple substance silicon nanowires accounts for elemental silicon
More than the 50% of nanowire cluster gross mass；In elemental silicon nanowire cluster structure, a diameter of 0.5um-100um simple substance silicon nanowires
The quality of group accounts for more than the 50% of elemental silicon nanowire cluster gross mass.
Above-mentioned conductive carbon material is the one or more in following middle macromolecule polymer material：Phenolic resin, pitch, Portugal
Grape sugar, sucrose, starch, fine polypropylene, polymethyl methacrylate, polyvinyl chloride；Or the conductive carbon material is by following gas
One or a combination set of the carbon material that changes into：Methane gas, ethane gas, propane flammable gas, propylene gas, acetylene gas, propine gas.
The preparation method of above-mentioned flocculence elemental silicon nanowire cluster, comprises the following steps：
(1) purity is put into the reactor in steam reaction stove for 98%-99.9999% HIGH-PURITY SILICON, uses reactor
Interior plasma torch heats HIGH-PURITY SILICON into gaseous state HIGH-PURITY SILICON, and gaseous state HIGH-PURITY SILICON is entered in growth controller by pipeline to be grown
Into the flocculence elemental silicon nanowire cluster of control size, flocculence elemental silicon nanowire cluster together passes through with the gas in reactor
Pipeline enters the flocculence elemental silicon nanowire cluster for obtaining solid-state in collector through gas solid separation, the pipe of collector gas outlet connection
Vavuum pump, air exhauster, heat exchanger are communicated with road, the cooling gas after heat exchanger passes through reacting furnace and reactor inner chamber
Connection, the discharging opening of storage vat both passes through reactor with the feed pipe of growth controller and connected with reactor inner chamber；Described life
The anterior feed pipe of long controller is that preceding feed pipe, the discharge pipe at rear portion are rear discharge nozzle, preceding feed pipe length and growth
The ratio between controller internal diameter is (0.1-10)：1, the length of preceding feed pipe refers to that reactor wall enters intraoral towards growth controller
The ratio between the duct length of wall, preceding feed pipe internal diameter and growth controller internal diameter are (0.05-0.8)：1；Passed in and out by control material
Flow, flow direction and the cooling velocity of growth controller are to control the agglomerating size of flocculence elemental silicon nanowire cluster, so as to obtain
It is required that flocculence elemental silicon nanowire cluster；
(2) collector discharging valve port is opened, flocculence elemental silicon nanowire cluster is taken out；Flocculence elemental silicon nanowire cluster
Purity is 98%-99.9999%.
A kind of preparation method of flocculence elemental silicon nanowire cluster/carbon compound cathode materials comprises the following steps：
(1) prepared polymer solution：Elemental silicon nanowire cluster and middle high molecular polymer are weighed, elemental silicon nanowire cluster is accounted for
10%-90%, middle high molecular polymer mass percent accounts for 10%-90%, the middle high molecular polymer weighed is dissolved in molten
In agent, 1-30wt% polymer solution is obtained；
(2) the elemental silicon nanowire cluster for weighing step (1) is fitted into the middle macromolecule polymer solution of step (1) making
Carry out the dispersed mixing of mechanical agitation or machinery emulsification dispersion mixing or ultrasound dispersed is mixed to get mixed liquor；
(3) mixed liquor for preparing step (2), is evacuated to 150-350 DEG C, in 100-500kpa pressure vessel, further
Dispersed mixing, makes middle high molecular polymer preferably coat elemental silicon nanowire cluster and is uniformly mixed liquid；
(4) the uniform mixed liquor for preparing step (3) is dried by solvent filter or after drying or filtering and obtains mixture
Material.
(5) it is carbonized：Mixed liquor prepared by step (4) is fitted into material boat, is put into heating reaction furnace in inert gas
Protection under fire be heated to 900-1600 DEG C of temperature and carburizing reagent processing carried out to mixture in 2-24 hours, it is then natural
It is cooled to less than 200 DEG C or to the material after carburizing reagent, then size-reduced, sieving after air natural temperature, is taken out, obtains cotton-wool
Shape elemental silicon nanowire cluster/carbon compound cathode materials.
Above-mentioned reacting furnace is one of vacuum tube furnace, rotary furnace, roller-way cellar for storing things, push pedal cellar for storing things, heating response equipment；Described
Inert gas is one or a combination set of nitrogen, neon, argon gas, helium.
Flocculence elemental silicon nanowire cluster/carbon compound cathode materials pole material is used for the GND of lithium battery.
Above-mentioned lithium battery includes anode, GND, electrolyte and barrier film, and described GND is with described
Lithium cell cathode material be made.
The present invention is prominent and beneficial compared with prior art to be had the technical effect that：
1st, elemental silicon (Si) the flocculence nanowire cluster prepared by the present invention is in physical vapor (PVD) vacuum tightness environment bar
Growth shaping under part, is not used without any chemical substance, and any pollution is not caused to atmospheric environment and soil.
2nd, the flocculence elemental silicon nanowire cluster prepared by the present invention is to solve silicon materials in lithium ion battery negative material
The material space problem of internal stress without release in the coefficient of expansion problem and expansion process during discharge and recharge deintercalation, it is to avoid silicon
The crushing of material, the board construction caused is destroyed (such as blast).
3rd, the flocculence elemental silicon nanowire cluster prepared by the present invention, its individual particle size is right in 0.5um-100um (Fig. 2)
Its decentralized processing is extremely easy, and carbon source material also easily carries out appearance cladding to it.If nano-silicon individual particle size is in 20-
100nm, although significantly reduce expansion rate problem, but its because individual particle size it is too small, pole is difficult dispersed, causes carbon source material
Material is difficult the uniform cladding problem to its appearance.
4th, the lithium ion battery negative material for the Novel high-specific capacity flexible that the present invention is developed, pitch softening is carried out to nano-silicon and is wrapped
Cover, silicon grain can be avoided directly to be contacted with electrolyte, slow down capacity attenuation speed, while the diffusion path of lithium ion is shortened,
Ensure that the electronics conduction of electrode material will not lose, that is, improve first charge-discharge efficiency, charge/discharge capacity and cycle performance.
Brief description of the drawings
Fig. 1 is the electron microscope observation photo of the simple substance silicon nanowires of the present invention.
Fig. 2 is the electron microscopic of the elemental silicon nanowire cluster for the flocculence structure that the present invention is combined into simple substance silicon nanowires
Sem observation photo.
Fig. 3 is that the lithium ion battery initial charge specific capacity that the embodiment of the present invention 1 makes reaches 2392mAh/g, is put first
Electric specific capacity 2033mAh/g, the specific discharge capacity of 100 cycle charge-discharges and relation curve (solid line) figure of discharge time, figure
Middle dotted line is instruction line.
Fig. 4 is that the lithium ion battery initial charge specific capacity that the embodiment of the present invention 4 makes reaches 1768mAh/g, is put first
Electric specific capacity 1415mAh/g, the specific discharge capacity of 100 cycle charge-discharges and relation curve (solid line) figure of discharge time, figure
Middle dotted line is instruction line.
Fig. 5 is that the electron microscope of the elemental silicon nanowire cluster for the flocculence structure being combined into simple substance nano silicon particles is seen
Examine one of photo.
Fig. 6 is that the electron microscope of the elemental silicon nanowire cluster for the flocculence structure being combined into simple substance nano silicon particles is seen
Examine the two of photo.
Fig. 7 is the electron microscopic of the multiple elemental silicon nanowire clusters for the flocculence structure being combined into simple substance nano silicon particles
Sem observation photo, to show that elemental silicon nanowire cluster has different sizes.
Embodiment
Referring to Fig. 1-Fig. 7：
A kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials, a kind of elemental silicon nanowire cluster is to use elemental silicon
Conductive carbon material is coated with the flocculence structure that nano wire is combined into, the outer surface and its space of elemental silicon nanowire cluster or mixed
Close at least a kind of conductive material in conductive material formation lithium ion battery negative material, described hybrid conductive material.
Above-mentioned elemental silicon nanowire cluster is the flocculence structure being combined into simple substance nano silicon particles, simple substance silicon nanowires
Conductive carbon material or hybrid conductive material formation lithium ion battery negative material are coated with the outer surface and its space of group, it is described
Hybrid conductive material at least a kind of conductive material.
Above-mentioned elemental silicon nanowire cluster is the flocculence knot being combined into simple substance nano silicon particles and simple substance silicon nanowires
Conductive carbon material or hybrid conductive material formation lithium-ion electric are coated with structure, the outer surface and its space of elemental silicon nanowire cluster
At least a kind of conductive material in pond negative material, described hybrid conductive material.
In above-mentioned elemental silicon nanowire cluster structure, the quality of a diameter of 15nm-300nm simple substance silicon nanowires accounts for elemental silicon
More than the 50% of nanowire cluster gross mass；In elemental silicon nanowire cluster structure, a diameter of 0.5um-100um simple substance silicon nanowires
The quality of group accounts for more than the 50% of elemental silicon nanowire cluster gross mass.
Above-mentioned conductive carbon material is the one or more in following middle macromolecule polymer material：Phenolic resin, pitch, Portugal
Grape sugar, sucrose, starch, fine polypropylene, polymethyl methacrylate, polyvinyl chloride；Or the conductive carbon material is by following gas
One or a combination set of the carbon material that changes into：Methane gas, ethane gas, propane flammable gas, propylene gas, acetylene gas, propine gas.
The preparation method of above-mentioned flocculence elemental silicon nanowire cluster, comprises the following steps：
(1) purity is put into the reactor in steam reaction stove for 98%-99.9999% HIGH-PURITY SILICON, uses reactor
Interior plasma torch heats HIGH-PURITY SILICON into gaseous state HIGH-PURITY SILICON, and gaseous state HIGH-PURITY SILICON is entered in growth controller by pipeline to be grown
Into the flocculence elemental silicon nanowire cluster of control size, flocculence elemental silicon nanowire cluster together passes through with the gas in reactor
Pipeline enters the flocculence elemental silicon nanowire cluster for obtaining solid-state in collector through gas solid separation, the pipe of collector gas outlet connection
Vavuum pump, air exhauster, heat exchanger are communicated with road, the cooling gas after heat exchanger passes through reacting furnace and reactor inner chamber
Connection, the discharging opening of storage vat both passes through reactor with the feed pipe of growth controller and connected with reactor inner chamber；Described life
The anterior feed pipe of long controller is that preceding feed pipe, the discharge pipe at rear portion are rear discharge nozzle, preceding feed pipe length and growth
The ratio between controller internal diameter is (0.1-10)：1, the length of preceding feed pipe refers to that reactor wall enters intraoral towards growth controller
The ratio between the duct length of wall, preceding feed pipe internal diameter and growth controller internal diameter are (0.05-0.8)：1；Passed in and out by control material
Flow, flow direction and the cooling velocity of growth controller are to control the agglomerating size of flocculence elemental silicon nanowire cluster, so as to obtain
It is required that flocculence elemental silicon nanowire cluster；
(2) collector discharging valve port is opened, flocculence elemental silicon nanowire cluster is taken out；Flocculence elemental silicon nanowire cluster
Purity is 98%-99.9999%.
Described reactor is made of to use exotic material exotic material such as zirconium oxide, graphite, quartz, alloy
Vessels crucible.
A kind of preparation method of flocculence elemental silicon nanowire cluster/carbon compound cathode materials comprises the following steps：
(1) prepared polymer solution：Elemental silicon nanowire cluster and middle high molecular polymer are weighed, elemental silicon nanowire cluster is accounted for
10%-90%, middle high molecular polymer mass percent accounts for 10%-90%, the middle high molecular polymer weighed is dissolved in molten
In agent, 1-30wt% polymer solution is obtained；
(2) the elemental silicon nanowire cluster for weighing step (1) is fitted into the middle macromolecule polymer solution of step (1) making
Carry out the dispersed mixing of mechanical agitation or machinery emulsification dispersion mixing or ultrasound dispersed is mixed to get mixed liquor；
(3) mixed liquor for preparing step (2), is evacuated to 150-350 DEG C, in 100-500kpa pressure vessel, further
Dispersed mixing, makes middle high molecular polymer preferably coat elemental silicon nanowire cluster and is uniformly mixed liquid；
(4) the uniform mixed liquor for preparing step (3) is dried by solvent filter or after drying or filtering and obtains mixture
Material.
(5) it is carbonized：Mixed liquor prepared by step (4) is fitted into material boat, is put into heating reaction furnace in inert gas
Protection under fire be heated to 900-1600 DEG C of temperature and carburizing reagent processing carried out to mixture in 2-24 hours, it is then natural
It is cooled to less than 200 DEG C or to the material after carburizing reagent, then size-reduced, sieving after air natural temperature, is taken out, obtains cotton-wool
Shape elemental silicon nanowire cluster/carbon compound cathode materials.
Above-mentioned reacting furnace is one of vacuum tube furnace, rotary furnace, roller-way cellar for storing things, push pedal cellar for storing things, heating response equipment；Described
Inert gas is one or a combination set of nitrogen, neon, argon gas, helium.
Flocculence elemental silicon nanowire cluster/carbon compound cathode materials pole material is used for the GND of lithium battery.
Above-mentioned lithium battery includes anode, GND, electrolyte and barrier film, and described GND is with described
Lithium cell cathode material be made.
In order to be better understood from the present invention, with specific embodiment, the invention will be further described below in conjunction with the accompanying drawings, but
It is that, in order to easily read, partial content has done simplified processing, detailed process see above：
Embodiment 1：
Weigh 2 grams of high temperature asphalt (offer of Johanna Lüttge (Shanghai) trade Co., Ltd) to be dissolved in 150ML ethanol, obtain
Polymer solution, adds 4 grams of flocculence elemental silicon nanowire clusters, carries out the scattered stirring mixing 10min- of machinery emulsification
120min, makes the fully dispersed mixing of flocculence elemental silicon nanowire cluster in a polymer solution, will obtain fully dispersed uniform
Mixture solution, which is evacuated in high temperature pressure vessel further dispersion mixing, uniformly, makes asphalt mixture solution more preferably be coated on cotton
Cotton-shaped elemental silicon nanowire cluster.
By the solvent filter in high temperature pressure vessel, thick mixture, as high temperature asphalt cladding cotton are obtained
Cotton-shaped elemental silicon nanowire cluster composite, is transferred in blowing boat, under argon gas atmosphere protection, loads electron tubes type heating
Stove heat is incubated 4 hours to 1150 DEG C, and pitch sends carburizing reagent in the process, and 5.9 composite is taken out after cooling,
Size-reduced again, sieving, obtains flocculence elemental silicon nanowire cluster/carbon compound cathode materials.
It is 68% to measure flocculence elemental silicon nanowire cluster content in the composite negative pole material by thermogravimetric analyzer.
By resulting flocculence elemental silicon nanowire cluster/carbon compound cathode materials respectively with conductive agent acetylene black, bond
Agent PVDF by mass percentage 79:10:11 mixing, wherein weighing flocculence elemental silicon nanowire cluster/carbon compound cathode materials
2.37g, acetylene black 0.3g, PVDF0.33g, are tuned into slurry, uniformly with NMP (1- methyl -2- pyrroles cyclic ketones) by thing mixed above
It is coated on Copper Foil, 110 ° are dried in vacuo 20 hours, and experiment battery pole piece, using lithium piece as counter electrode, electrolyte is made
1mol/L, LIPEC EC (ethyl carbonate ester)+DMC (dimethyl carbonate) volume ratio 1:1 solution, barrier film is Lelgard2400
Film, is assembled into CR2025 button cells in the glove box full of argon gas atmosphere.
As shown in figure 3, the battery as made by this example, initial charge specific capacity reaches 2392mAh/g, the ratio of electric discharge first
Capacity 2033mAh/g, second of charge specific capacity reaches 1913mAh/g, and second of specific discharge capacity is 1735mAh/g.
This, which is mainly in discharge process first, generates solid electrolyte membrane (SEI) film and part irreversible reaction, such as portion
The hollow cotton particle of simple substance silicon nanowires for dividing carbon uncoated, splits and comes off, have a small amount of oxygen to be generated combined with lithium in composite
Caused by lithia.But first with the increase of cycle-index after impulse electricity, battery special capacity fade is not obvious, 100 times
Discharge capacity stills remain in 1659mAh/g after circulation, outside the carbon for illustrating flocculence elemental silicon nanowire cluster/carbon composite
Shell effectively inhibits the Volumetric expansion of silicon, improves the cycle performance of lithium ion battery.
Embodiment 2：
(1) 2 grams of high temperature asphalt (offer of Johanna Lüttge (Shanghai) trade Co., Ltd) are weighed to be dissolved in 150ML ethanol,
Polymer solution is obtained, 2 grams of flocculence elemental silicon nanowire clusters are added, the scattered stirring mixing 10min- of machinery emulsification is carried out
120min, makes the fully dispersed mixing of flocculence elemental silicon nanowire cluster in a polymer solution, will obtain fully dispersed uniform
Mixture solution, which is evacuated in high temperature pressure vessel further dispersion mixing, uniformly, makes asphalt mixture solution more preferably be coated on cotton
Cotton-shaped elemental silicon nanowire cluster.
(2) by the solvent filter in high temperature pressure vessel, thick mixture is obtained, as high temperature asphalt is coated
Flocculence elemental silicon nanowire cluster composite, is transferred in blowing porcelain boat, under argon gas atmosphere protection, loads electron tubes type
Heating furnace is heated to 1150 DEG C, is incubated 4 hours, and pitch sends carburizing reagent in the process, and 3.9 grams of taking-up is porous after cooling leads
Electrical carbon coats flocculence elemental silicon nanowire cluster composite.
(3) it is 52% to measure composite elemental silicon containing the flocculence nanowire cluster content by thermogravimetric analyzer.
(4) by resulting flocculence elemental silicon nanowire cluster/carbon compound cathode materials respectively with conductive agent acetylene black, glue
Tie agent PVDF by mass percentage 79:10:11 mixing, wherein the hollow cotton of simple substance silicon nanowires/carbon negative pole material 2.37g is weighed,
Acetylene black 0.3g, PVDF0.33g, are tuned into slurry by thing mixed above with NMP (1- methyl -2- pyrroles cyclic ketones), are coated uniformly on
On Copper Foil, 110 ° are dried in vacuo 20 hours, and experiment battery pole piece is made, using lithium piece as counter electrode, electrolyte 1mol/L,
LIPEC EC (ethyl carbonate ester)+DMC (dimethyl carbonate) volume ratio 1:1 solution, barrier film is Lelgard2400 films, is being filled
CR2025 button cells are assembled into the glove box of full argon gas atmosphere.
(5) battery as made by this example, initial charge specific capacity reaches 1885mAh/g, first discharge specific capacity
1658.8mAh/g, second of charge specific capacity reaches 1715mAh/g, and second of electric discharge is than being 1542mAh/g.
This, which is mainly in discharge process first, generates solid electrolyte membrane (SEI) film and part irreversible reaction, such as portion
The hollow cotton particle of simple substance silicon nanowires for dividing carbon uncoated, splits and comes off, have sales volume oxygen to be generated combined with lithium in composite
Caused by lithia.But first with the increase of cycle-index after impulse electricity, battery special capacity fade is not obvious, 100 times
Discharge capacity stills remain in 1563mAh/g after circulation, outside the carbon for illustrating flocculence elemental silicon nanowire cluster/carbon composite
Shell effectively inhibits the Volumetric expansion of silicon, improves the cycle performance of lithium ion battery.
Embodiment 3：
(1) weigh 85% glucose of concentration 2 grams (market supplies) and be dissolved in 120ml ethanol, form glucose solution, add
4 grams of flocculence elemental silicon nanowire clusters simultaneously stir, and glucose solution is more preferably coated on flocculence elemental silicon nanowire cluster；
(2) 5.7 grams of carbon coating flocculence elemental silicon nanowire clusters, then size-reduced, sieving are taken out after being carbonized and cooling down, is obtained
Flocculence elemental silicon nanowire cluster/carbon compound cathode materials；
(3) wherein：Flocculence elemental silicon nanowire cluster content is 70%；
(4) by resulting flocculence elemental silicon nanowire cluster/carbon compound cathode materials respectively with conductive agent acetylene black, glue
Tie agent PVDF by mass percentage 79:10:11, weigh flocculence elemental silicon nanowire cluster/carbon compound cathode materials 2.37g, second
Acetylene black 0.3g, PVDF0.33g, are tuned into slurry by thing mixed above with NMP (1- methyl -2- pyrroles cyclic ketones), are coated uniformly on copper
On paper tinsel, 110 ° are dried in vacuo 20 hours, and experiment battery pole piece is made, using lithium piece as counter electrode, electrolyte 1mol/L,
LIPEC EC (ethyl carbonate ester)+DMC (dimethyl carbonate) volume ratio 1:1 solution, barrier film is Lelgard2400 films, is being filled
CR2025 button cells are assembled into the glove box of full argon gas atmosphere；
(5) battery as made by present case, initial charge specific capacity reaches 2420mAh/g, first discharge specific capacity
1985mAh/g, second of charge specific capacity reaches 1936mAh/g, and second of electric discharge is than for 1645.6mAh/g., this is mainly first
Solid electrolyte membrane (SEI) film and part irreversible reaction are generated in discharge process, such as uncoated elemental silicon of part carbon is received
The hollow cotton particle of rice noodles, splits and comes off, caused by having sales volume oxygen to generate lithia combined with lithium in composite.But rush first
With the increase of cycle-index after electric discharge, battery special capacity fade is not obvious, and discharge capacity is remained in that after 100 circulations
In 1563mAh/g, illustrate that the carbon shell of flocculence elemental silicon nanowire cluster/carbon composite effectively inhibits the volume of silicon swollen
Swollen effect, improves the cycle performance of lithium ion battery.
Embodiment 4：
(1) weigh 85% glucose of concentration 2 grams (market supplies) and be dissolved in 120ml ethanol, form glucose solution, add
2 grams of flocculence elemental silicon nanowire clusters simultaneously stir, and glucose solution is more preferably coated on flocculence elemental silicon nanowire cluster；
(2) 3.7 grams of carbon coating flocculence elemental silicon nanowire clusters, then size-reduced, sieving are taken out after being carbonized and cooling down, is obtained
Flocculence elemental silicon nanowire cluster/carbon compound cathode materials；
(3) wherein：Flocculence elemental silicon nanowire cluster content is 54%；
(4) by resulting flocculence elemental silicon nanowire cluster/carbon compound cathode materials respectively with conductive agent acetylene black, glue
Tie agent PVDF by mass percentage 79:10:11, weigh flocculence elemental silicon nanowire cluster/carbon compound cathode materials 2.37g, second
Acetylene black 0.3g, PVDF0.33g, are tuned into slurry by thing mixed above with NMP (1- methyl -2- pyrroles cyclic ketones), are coated uniformly on copper
On paper tinsel, 110 ° are dried in vacuo 20 hours, and experiment battery pole piece is made, using lithium piece as counter electrode, electrolyte 1mol/L,
LIPEC EC (ethyl carbonate ester)+DMC (dimethyl carbonate) volume ratio 1:1 solution, barrier film is Lelgard2400 films, is being filled
CR2025 button cells are assembled into the glove box of full argon gas atmosphere；
(5) as shown in figure (4), the battery as made by present case, initial charge specific capacity reaches 1768mAh/g, first
Specific discharge capacity 1415mAh/g, second of charge specific capacity reaches 1502.8mAh/g, and second of specific discharge capacity is 1203mAh/
G, this, which is mainly in discharge process first, generates solid electrolyte membrane (SEI) film and part irreversible reaction, such as part carbon not
Flocculence elemental silicon nanowire cluster/carbon compound cathode materials of cladding, split and come off, and are to have in composite a small amount of oxygen can be with lithium
Caused by generation lithia.But first with the increase of cycle-index after impulse electricity, battery special capacity fade is simultaneously failed to understand
Aobvious, discharge capacity stills remain in 1118mAh/g after 100 circulations, illustrates flocculence elemental silicon nanowire cluster/carbon composite wood
The carbon shell of material effectively inhibits the Volumetric expansion of silicon, improves the cycle performance of lithium ion battery.
Above-described embodiment is only presently preferred embodiments of the present invention, is not limited the scope of the invention according to this, therefore：It is all according to
The equivalence changes that the structure of the present invention, shape, principle are done, all should be covered by within protection scope of the present invention.
Claims (10)
1. a kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials, it is characterised in that：Described elemental silicon nanowire cluster
It is to be coated with conduction in the flocculence structure being combined into simple substance silicon nanowires, the outer surface and its space of elemental silicon nanowire cluster
It is at least a kind of conductive in carbon material or hybrid conductive material formation lithium ion battery negative material, described hybrid conductive material
Material.
2. a kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials according to claim 1, it is characterised in that：
Described elemental silicon nanowire cluster is the flocculence structure being combined into simple substance nano silicon particles, the appearance of elemental silicon nanowire cluster
Conductive carbon material or hybrid conductive material formation lithium ion battery negative material are coated with face and its space, described mixing is led
At least a kind of conductive material in electric material.
3. a kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials according to claim 1, it is characterised in that：
Described elemental silicon nanowire cluster is the flocculence structure being combined into simple substance nano silicon particles and simple substance silicon nanowires, elemental silicon
Conductive carbon material or hybrid conductive material formation lithium ion battery negative material are coated with the outer surface and its space of nanowire cluster
At least a kind of conductive material in material, described hybrid conductive material.
4. a kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials according to claim 1-3 any one, its
It is characterised by, in the elemental silicon nanowire cluster structure, the quality of a diameter of 15nm-300nm simple substance silicon nanowires accounts for simple substance
More than the 50% of silicon nanowires group's gross mass；In elemental silicon nanowire cluster structure, a diameter of 0.5um-100um elemental silicon nanometer
The quality of a ball of string accounts for more than the 50% of elemental silicon nanowire cluster gross mass.
5. a kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials according to claim 1-3 any one, its
It is characterised by, the conductive carbon material is the one or more in following middle macromolecule polymer material：Phenolic resin, pitch,
Glucose, sucrose, starch, polypropylene are fine, polymethyl methacrylate, polyvinyl chloride；Or the conductive carbon material is by following gas
The carbon material that one or a combination set of body is changed into：Methane gas, ethane gas, propane flammable gas, propylene gas, acetylene gas, propine gas.
6. a kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials according to claim 1-3 any one, its
It is characterised by：The preparation method of the flocculence elemental silicon nanowire cluster comprises the following steps：
(1) purity is put into the reactor in steam reaction stove for 98%-99.9999% HIGH-PURITY SILICON, with reactor
Plasma torch heats HIGH-PURITY SILICON into gaseous state HIGH-PURITY SILICON, and gaseous state HIGH-PURITY SILICON is entered in growth controller by pipeline grows into control
The flocculence elemental silicon nanowire cluster of size processed, flocculence elemental silicon nanowire cluster together passes through pipeline with the gas in reactor
Obtained in into collector through gas solid separation on the flocculence elemental silicon nanowire cluster of solid-state, the pipeline of collector gas outlet connection
Vavuum pump, air exhauster, heat exchanger are communicated with, the cooling gas after heat exchanger connects through reacting furnace with reactor inner chamber
Logical, the discharging opening of storage vat both passes through reactor with the feed pipe of growth controller and connected with reactor inner chamber；Described growth
The anterior feed pipe of controller is that preceding feed pipe, the discharge pipe at rear portion are rear discharge nozzle, and preceding feed pipe length is controlled with growth
The ratio between device internal diameter processed is (0.1-10)：1, the ratio between preceding feed pipe internal diameter and growth controller internal diameter are (0.05-0.8)：1；Pass through
Control material passes in and out flow, flow direction and the cooling velocity of growth controller to control the agglomerating big of flocculence elemental silicon nanowire cluster
It is small, so that desired flocculence elemental silicon nanowire cluster；
(2) collector discharging valve port is opened, flocculence elemental silicon nanowire cluster is taken out；The purity of flocculence elemental silicon nanowire cluster
For 98%-99.9999%.
7. a kind of flocculence elemental silicon nanowire cluster/carbon compound cathode materials according to claim 1-3 any one
Preparation method, it is characterised in that：Comprise the following steps：
(1) prepared polymer solution：Elemental silicon nanowire cluster and middle high molecular polymer are weighed, elemental silicon nanowire cluster is accounted for
10%-90%, middle high molecular polymer mass percent accounts for 10%-90%, the middle high molecular polymer weighed is dissolved in molten
In agent, 1-30wt% polymer solution is obtained；
(2) mixed once：The elemental silicon nanowire cluster that step (1) is weighed is fitted into the middle high molecular polymer of step (1) making
The dispersed mixing of mechanical agitation or machinery emulsification dispersion mixing are carried out in solution or ultrasound dispersed is mixed to get mixed liquor；
(3) secondary mixing：Mixed liquor prepared by step (2), is evacuated to 150-350 DEG C, in 100-500kpa pressure vessel, enters
The dispersed mixing of one step, makes middle high molecular polymer preferably coat elemental silicon nanowire cluster and is uniformly mixed liquid；
(4) filtering is dried：Uniform mixed liquor prepared by step (3) is dried by solvent filter or after drying or filtering and mixed
Compound material.
(5) it is carbonized：Mixed liquor prepared by step (4) is fitted into material boat, is put into heating reaction furnace in the guarantor of inert gas
The lower fire of shield is heated to 900-1600 DEG C of temperature and carries out carburizing reagent processing to mixture in 2-24 hours, then Temperature fall
To less than 200 DEG C or to the material after carburizing reagent, then size-reduced, sieving after air natural temperature, is taken out, flocculence list is obtained
Matter silicon nanowires group/carbon compound cathode materials.
8. a kind of preparation method of flocculence elemental silicon nanowire cluster/carbon compound cathode materials according to claim 7, its
It is characterised by：Described reacting furnace is one of vacuum tube furnace, rotary furnace, roller-way cellar for storing things, push pedal cellar for storing things, heating response equipment；It is described
Inert gas one or a combination set of for nitrogen, neon, argon gas, helium.
9. with a kind of preparation side of flocculence elemental silicon nanowire cluster/carbon compound cathode materials pole material described in claim 7
The purposes of flocculence elemental silicon nanowire cluster/carbon compound cathode materials prepared by method, it is characterised in that：Battery for lithium battery
Negative pole.
10. such as the purposes of claim 9 flocculence elemental silicon nanowire cluster/carbon compound cathode materials, it is characterised in that：Described
Lithium battery includes anode, GND, electrolyte and barrier film, and described GND is with described lithium ion battery anode material
What material was made.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106935811A (en) * | 2015-12-30 | 2017-07-07 | 友达晶材股份有限公司 | Lithium battery negative electrode material and method for producing same |
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| CN112599758A (en) * | 2021-03-03 | 2021-04-02 | 拓米(成都)应用技术研究院有限公司 | Nano silicon aggregate composite negative electrode material and preparation method thereof |
| CN112599758B (en) * | 2021-03-03 | 2021-07-06 | 拓米(成都)应用技术研究院有限公司 | Nano silicon aggregate composite negative electrode material and preparation method thereof |
| CN114180577A (en) * | 2021-11-30 | 2022-03-15 | 陕西科技大学 | Silicon nanowire array and preparation method thereof |
| CN114180577B (en) * | 2021-11-30 | 2023-02-28 | 陕西科技大学 | Silicon nanowire array and preparation method thereof |
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