CN106450208B - A kind of silicon composite and preparation method thereof for cathode of lithium battery - Google Patents
A kind of silicon composite and preparation method thereof for cathode of lithium battery Download PDFInfo
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- CN106450208B CN106450208B CN201610960786.0A CN201610960786A CN106450208B CN 106450208 B CN106450208 B CN 106450208B CN 201610960786 A CN201610960786 A CN 201610960786A CN 106450208 B CN106450208 B CN 106450208B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The silicon composite and preparation method thereof that the present invention provides a kind of for cathode of lithium battery.The silicon composite is three-dimensional net structure, including nanometer elementary silicon and aerosil, nanometer elementary silicon are embedded in the micropore of aerosil.The preparation method the following steps are included: be 1:(0.3-1 by organosilicate, inorganic silicate, polyvinyl alcohol and water in mass ratio): (0.1-0.2): (3-7) is mixed, acid is added dropwise, then simple substance nano silica fume is added, ammonium hydroxide is added dropwise, 20min-40min is kept the temperature under the conditions of 50 DEG C -80 DEG C again, then it is mixed with composition, foam, foamable, obtains a nanometer elementary silicon/aerosil.Nanometer elementary silicon can be fixed in the micropore of aerosil by silicon composite provided by the invention, and can make the being consistent property of expansion or shrinkage of aeroge and silicon, prevented powdered phenomenon caused by silicon volume expansion, improved the cycle performance of lithium battery.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, are related to a kind of silicon composite wood for cathode of lithium battery
Material and preparation method thereof.
Background technique
The energy is the important material base of human survival and development, is motive power and the society for being engaged in various economic activities
The important symbol of the meeting level of economic development.With fossil fuel peter out and the problems such as global warming brought by it, it is many
More researchers start gradually to pay close attention to New Energy Industry.Wherein, lithium ion battery is high with its operating voltage, specific energy is big, it is light-weight,
It is small in size, have extended cycle life, memory-less effect, can be quickly charged and discharged with a series of significant advantages such as non-environmental-pollution into being
The research hotspot of new energy field.
Currently, the lithium ion battery of commercialization mainly uses graphite carbon material as negative electrode active material.But due to
The specific capacity of carbons negative electrode material is lower (372mAh/g), and current lithium ion battery is difficult to meet the big of automobile-used lithium ion battery
The requirement such as power, high capacity, it is, thus, sought for a kind of negative electrode material of height ratio capacity reduces the usage amount of negative electrode material,
Improve the capacity and power of lithium ion battery.
Silica-base material is the negative electrode material that can satisfy lithium ion battery requirement of new generation at present.With carbons negative electrode material phase
Than the specific capacity of silicon is higher, and theoretical capacity may be up to 4200mAh/g, is the ideal material for substituting graphite-like electrode.But by
In silicon during charge and discharge, violent variation can occur for volume, and the structure of material can be destroyed, and lead to lithium ion battery
Capacity attenuation, electrode cycle is unstable, or even causes battery failure.Therefore, the volume expansion for how overcoming the problems, such as silicon materials, mentions
Its high cyclical stability is the emphasis of silicon based anode material research.It is devoted to improve and optimize silicon there are many research at present
In the performance of base negative electrode material, for example, silicon particle dispersion is in the porous material or compound etc. by silicon and other materials.There is research
Nano thin-film, nanotube or nano wire are prepared using magnetron sputtering, evaporation electroplating method, the nanocrystallization technology of silicon materials is realized, subtracts
Volumetric expansion of few silicon materials in embedding lithium/de- lithium process (charge and discharge process).As patent application CN101393980A is public
Silicium cathode and lithium ion secondary battery and their preparation method including the cathode have been opened, magnetically controlled sputter method is used to prepare
The lithium ion battery negative material of carbon material layer and silicon layer composition, the negative electrode material volume and capacity ratio with higher obtained.
Patent application CN103943821A discloses cathode, the battery with the cathode and cathode preparation method, passes through magnetron sputtering
Silicon particles and/or silicon films are deposited on a current collector, prepare negative electrode of lithium ion battery, and the negative electrode material of acquisition has bigger serface
Collector, and capacity is big, good conductivity.But the negative electrode material of physical method preparation is easy to happen in charge and discharge process
Falling off for active material, decays quickly so as to cause battery capacity, poor circulation.Also there is research that silicon is prepared into porous material
Improve the performance of silicon based anode material, as patent application CN104577049A discloses a kind of lithium battery hierarchical porous structure silicon
Multi-stage porous knot is made using ultrafine silica powder waste in optical fiber production process for base negative electrode material and preparation method thereof
Structure silicon based anode material increases the extension space of the volume expansion of silicon materials in the lithium storage process, alleviates the body during storage lithium
Product effect, alleviates mechanical stress, improves the cyclical stability of lithium ion battery.In addition, there are also researchs to use chemical vapor deposition
(CVD) method prepares the compound system for wrapping up amorphous carbon layer outside silicon particle and is applied to lithium ion battery negative material, this is compound
Although system improves the structure and electric conductivity of silicon materials to a certain extent, silicon in lithium ion charge and discharge process has been restrained
Bulk effect, improve cycle performance, but the process of CVD method is difficult to control, uncertain factor is more, therefore batch difficult to realize
Production.There are also researchs to use metal and the alloy of silicon formation as lithium ion battery negative material to reduce body in charge and discharge process
Product expansion rate.If patent application CN105680008A discloses a kind of preparation method and application of metal-modified porous silicon powder,
It uses metal assistant chemical etch preparation porous silicon powder and retains remaining assistant metal particle after corrosion, to increase silicon
Electric conductivity, the performance for improving lithium ion battery.But cathode material of the alloy formed using Si and metal as lithium ion battery
Material during lithium ion battery charge and discharge can and lithium form alloy, and generate the expansion and contraction of volume, cause metal atomization with
And the deterioration of cycle characteristics, the performance of lithium ion battery is influenced, in addition, there is also be not easy to be amorphous for Metal And Silicon alloy system
The problem of.Patent application CN102208634A discloses a kind of porous silicon/carbon composite material and preparation method thereof, using magnesium metal
The oxide of powder reduction silicon prepares porous silicon, and then using the carbonization of organic carbon source high temperature pyrolysis, packet carbon, preparation are more on porous silicon
Hole silicon/carbon composite, but silicon source, carbon source are all from chemical industry synthesis, higher cost.Patent application CN102237519A is disclosed
Three-dimensional porous silica powder anode material of lithium ion battery fluoride-free preparation method, by by common micron silicon, magnesium granules chemical combination
Reaction generates magnesium silicide, is then at high temperature pyrolyzed magnesium silicide, forms magnesium steam and the silicon with three-dimensional porous structure
Powder can obtain bulk effect to silicon particle and carry out certainly although the silicon powder material of the three-dimensional porous structure of preparation has porous structure
It absorbs, but cost of material is higher.
The method of these above-mentioned prior arts, has that expensive, process is complicated, is difficult to asking for large-scale production mostly
Topic, some even can also generate pollutant, and all only slow down the body of lithium ion battery charge and discharge process to a certain extent
It accumulates bulking effect or even some is to sacrifice lithium battery cycle performance as cost.Therefore, it is next to find a kind of new silica-base material
The requirement for meeting lithium ion battery negative material of new generation, is the important topic for breaking through Study on Li-ion batteries bottleneck at present.
Summary of the invention
The shortcomings that in view of the above-mentioned prior art, the purpose of the present invention is to provide a kind of silicon for cathode of lithium battery is compound
The preparation method of material.Nano-silicon is introduced during aerosil formation, to obtain silicon composite.It is special
Different network structure solves in existing lithium ion battery silicon cathode material charge and discharge process since Volumetric expansion causes to hold
The problem of amount decays rapidly.
To achieve the goals above, use the specific technical proposal is:
A kind of preparation method of the silicon composite for cathode of lithium battery, it is characterised in that the following steps are included:
Step 1: being 1:(0.3-1 by organosilicate, inorganic silicate, polyvinyl alcohol and water in mass ratio): (0.1-
0.2): (3-7) mixing obtains the first mixture, and it is 3-6 that acid solution is added dropwise in the first mixture of Xiang Suoshu and adjusts its pH, obtains
The thick solution of silica；
Step 2: carrying out centrifugation purification for the thick solution of the silica, and simple substance nano silica fume is then added, obtains second
Mixture, it is 7-9 that Xiang Suoshu second, which mixes species and ammonia spirit is added dropwise to adjust its pH, then carries out ultrasonic disperse, obtains nanometer
Elementary silicon/silica mixed sols presoma, wherein the simple substance nano-silicon powder and the mass ratio of the machine silicate are
1:(5-20), the partial size of the nanometer elementary silicon is 30 nm-, 80 nm；
Step 3: the nanometer elementary silicon/silica mixed sols presoma is kept the temperature under the conditions of 50 DEG C -80 DEG C
20min-40min obtains leather hard nanometer elementary silicon/silica mixed gel；
Step 4: by polyurethane nano particle, foaming agent, polymer emulsion, fluorocarbon surfactant in 1500-
The emulsified 30min-40min of 2500rpm speed conditions, obtains composition, foam；
Step 5: the composition, foam is mixed with the leather hard nanometer elementary silicon/silica mixed gel, so
Foamable at a temperature of normal pressure, 100 DEG C -120 DEG C afterwards, obtains a nanometer elementary silicon/aerosil, is classified through refinement
To the silicon composite for cathode of lithium battery.
The gas that above-mentioned preparation method is generated by composition, foam in foamable will have leather hard flexible to receive
Rice elementary silicon/silica mixed gel network gap struts completely, and it is micro- to form the more uniform aerosil of size
Pore structure, and make nanometer elementary silicon is particle studded to fix in the micropore, at the same can by the organic volatile in foaming agent at
Divide volatilization to exclude, obtains a nanometer elementary silicon/aerosil.
In the above preparation method, it is preferable that the organosilicate includes sodium methyl silicate or potassium methyl silicate；It is described
Inorganic silicate includes sodium metasilicate or potassium silicate.
In the above preparation method, it is preferable that the acid solution is inorganic acid solution or organic acid soln；
The inorganic acid be include any one of hydrochloric acid, sulfuric acid, phosphoric acid or hydrofluoric acid；
The organic acid includes any one of oxalic acid, acetic acid or citric acid.
In the above preparation method, it is preferable that the mass concentration of the acid solution is 5%-15%, the matter of the ammonia spirit
Amount concentration is 5%-15%.
In the above preparation method, it is preferable that the foaming agent includes azodicarbonamide, 4, the double benzene sulfonyls of 4 '-oxos
Hydrazine, benzene sulfonyl hydrazide, unifor, N, any one of N '-dinitrosopentamethlyene tetramine, ammonium hydrogen carbonate；
The polymer emulsion includes acrylamide, potassium acrylate, appointing in 2- acrylamido -2- methyl propane sulfonic acid
It is a kind of；
The fluorocarbon surfactant includes N, N- dihydroxy ethyl perfluoroalkyl amide, perfluoro caprylic acid ammonia, perfluor caproic acid ammonia,
Any one of perfluoroalkyl betain, perfluoroalkyl polyethers and perfluoroalkyl polyoxyethylene ether.
In the above preparation method, it is preferable that the polyurethane nano particle, foaming agent, polymer emulsion, fluorocarbon surface
The mass ratio of activating agent is 0.01:(5-8): (0.5-1): (0.02-0.05).
In the above preparation method, it is preferable that the composition, foam and the leather hard nanometer elementary silicon/silica
The mass ratio of mixed gel is 1:(80-95).
In the above preparation method, it is preferable that further include that vacuum is quiet before carrying out foamable in the step 5
The step of setting, the vacuum stand the specific steps are by the composition, foam and the leather hard nanometer elementary silicon/dioxy
The mixing of SiClx mixed gel, then stands 10min-15min under vacuum conditions.
In order to reach goal of the invention above-mentioned, the present invention provides a kind of silicon composite for cathode of lithium battery, special
Sign is the silicon composite for cathode of lithium battery prepared by the above method, and structure is that nanometer elementary silicon is embedded in titanium dioxide
The three-dimensional net structure formed in the micropore of silica aerogel.
Wherein, the partial size of the nanometer elementary silicon is 30 nm-, 80 nm；
The micropore size of the aerosil is 100 nm-200 nm.
Aeroge is to coalesce the light porous property nano structural material constituted, distinctive nano-scale by ultrafine dust
Grain makes it possess many unique properties with nano aperture structure, and aerosil has preferable mechanical performance, can be
In lithium ion battery charge and discharge process with the being consistent property of expansion or shrinkage of silicon, to effectively prevent making due to silicon volume expansion
At powdered phenomenon.
The present invention also provides the lithium ion batteries using above-mentioned silicon composite as negative electrode material.
The lithium ion battery includes battery case, pole piece and electrolyte, and the pole piece and electrolyte are sealingly received within described
In battery case, the pole piece includes anode, cathode and the diaphragm between positive electrode and negative electrode, the anode include collector and
The positive electrode of load on a current collector, the cathode includes the negative electrode material of collector and load on a current collector, described negative
Pole material is the silicon composite.
A kind of silicon composite and preparation method thereof for cathode of lithium battery of the present invention is dashed forward compared with prior art
Out the characteristics of and excellent effect are:
(1) provided by the present invention for the silicon composite of cathode of lithium battery, make using with high elasticity and buffering
Nanometer elementary silicon is fixed in the micropore of aerosil as carrier, makes lithium ion by the aerosil used
Battery is in charge and discharge process, the being consistent property of expansion or shrinkage of aerosil and silicon, to overcome existing lithium
The problem of causing capacity to decay rapidly due to Volumetric expansion in ion battery silicium cathode material charge and discharge process, improves lithium
The stability of ion battery cathode material and the cycle performance of battery, for new type lithium ion battery wide application provide it is new
Negative electrode material.
(2) provided by the present invention for the silicon composite of cathode of lithium battery, the three dimensional network of aerosil is utilized
The dimensional effect of network structure and nanometer elementary silicon improves the transmission performance of lithium ion；And nanometer elementary silicon/silica gas
Gel porosity with higher improves also it is possible to prevente effectively from silicon stereomutation effect causes to grind effect in cyclic process
Lithium ion battery cyclical stability；Silicon has specific capacity more higher than graphite simultaneously, can further obtain the charge and discharge for having high
The lithium ion battery of electric specific capacity and preferable cyclical stability.
(3) provided by the present invention for the preparation method of the silicon composite of cathode of lithium battery, by wet in silica
Polyvinyl alcohol is added when gel-forming, assigns gel certain flexibility, it is then that nano simple substance Si powder and silica is slightly molten
Liquid directly mixes, and by low-temperature heat, most of water equal solvent is excluded, it is mixed to form leather hard nanometer elementary silicon/silica
Close gel；Composition, foam is penetrated into the gel of leather hard, by foamable, keeps nanometer elementary silicon particle studded solid
In the fixed micropore, a nanometer elementary silicon/aerosil is obtained.In foamable, composition, foam will not volatilize immediately,
But it will be with certain flexibility as proppant under polyurethane nano particle, polymer emulsion, fluoro-carbon surface active effect
The net structure and pore size that collapse gap and support recovery aeroge original completely of leather hard gel, while can will foam
Volatile organic components in agent composition slowly volatilize exclusion.
(4) simple process, at low cost provided by the present invention for the preparation method of the silicon composite of cathode of lithium battery
It is honest and clean, can be mass-produced.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Present embodiments provide a kind of nanometer of elementary silicon/aerosil preparation method comprising following steps:
Step 1: with water in mass ratio it is that 1:1:0.1:7 is mixed by sodium methyl silicate, sodium metasilicate, polyvinyl alcohol, then drips
Adding mass concentration is 5% citric acid solution, and the pH for adjusting mixed system is 5, obtains the thick solution of silica；
Step 2: the thick solution of the silica is subjected to centrifugation purification with 6000rpm, part salt is removed, grain is then added
The simple substance nano silica fume that diameter is 30nm-80nm is mixed, while the ammonia spirit that mass concentration is 5% is added dropwise and adjusts mixture
The pH of system is 9, then carries out ultrasonic disperse, obtains a nanometer elementary silicon/silica mixed sols presoma, wherein simple substance is received
The mass ratio of sodium methyl silicate in rice silicon powder and step 1 is 1:5；
Step 3: nanometer elementary silicon/silica mixed sols presoma is kept the temperature into 40min under the conditions of 50 DEG C, is obtained
Leather hard nanometer elementary silicon/silica mixed gel；
Step 4: polyurethane nano particle, benzene sulfonyl hydrazide, the 2- acrylamide for being 0.01:5:0.8:0.03 by mass ratio
Base -2- methyl propane sulfonic acid, N, N- dihydroxy ethyl perfluoroalkyl amide are sent out in the emulsified 40min of 1500rpm speed conditions
Foaming composition；
Step 5: the composition, foam is mixed with leather hard nanometer elementary silicon/silica obtained in step 3 and is coagulated
Glue by 1:80 mass ratio mix, 10min-15min is then stood under 0.8MPa-1.5MPa vacuum condition, then normal pressure,
Foamable at a temperature of 100 DEG C will have leather hard nanometer elementary silicon/silica flexible to mix by the gas that foaming generates
The network gap for closing gel struts completely, forms the more uniform aerosil microcellular structure of size, and make nano-silicon list
Matter is particle studded to fix in the micropore, while the volatile organic components in foaming agent slowly being volatilized exclusion, is received
Rice elementary silicon/aerosil.
Nanometer elementary silicon/aerosil is made to the present embodiment to test, finds the close of the silicon composite
Degree is 350kg/m3, specific surface area is 500 m2/g 。
Nanometer elementary silicon/aerosil is made as the negative electrode material of lithium ion battery in the present embodiment, lithium is made
Ion battery, after lithium ion battery circulation after charge and discharge 500 times, capacity remains 90%.
Embodiment 2
Present embodiments provide a kind of nanometer of elementary silicon/aerosil preparation method comprising following steps:
Step 1: with water being that 1:0.8:0.2:5 is mixed by sodium methyl silicate, sodium metasilicate, polyvinyl alcohol, then in mass ratio
The acetum that mass concentration is 10% is added dropwise, the pH for adjusting mixed system is 4, obtains the thick solution of silica；
Step 2: the thick solution of the silica is subjected to centrifugation purification with 6000rpm, part salt is removed, grain is then added
The simple substance nano silica fume that diameter is 30nm-80nm is mixed, while the ammonia spirit that mass concentration is 10% is added dropwise and adjusts mixture
The pH of system is 8, then carries out ultrasonic disperse, obtains a nanometer elementary silicon/silica mixed sols presoma, wherein simple substance is received
The mass ratio of sodium methyl silicate in rice silicon powder and step 1 is 1:10；
Step 3: nanometer elementary silicon/silica mixed sols presoma is kept the temperature into 35min under the conditions of 60 DEG C, is obtained
Leather hard nanometer elementary silicon/silica mixed gel；
Step 4: polyurethane nano particle, azodicarbonamide, the acryloyl for being 0.01:6:0.5:0.05 by mass ratio
Amine, perfluoro caprylic acid ammonia obtain composition, foam in the emulsified 30min of 2000rpm speed conditions；
Step 5: the composition, foam is mixed with leather hard nanometer elementary silicon/silica obtained in step 3 and is coagulated
Glue by 1:85 mass ratio mix, 10min-15min is then stood under 0.8MPa-1.5MPa vacuum condition, then normal pressure,
Foamable at a temperature of 120 DEG C will have leather hard nanometer elementary silicon/silica flexible to mix by the gas that foaming generates
The network gap for closing gel struts completely, forms the more uniform aerosil microcellular structure of size, and make nano-silicon list
Matter is particle studded to fix in the micropore, while the volatile organic components in foaming agent slowly being volatilized exclusion, is received
Rice elementary silicon/aerosil.
Embodiment 3
Present embodiments provide a kind of nanometer of elementary silicon/aerosil preparation method comprising following steps:
Step 1: with water being that 1:0.6:0.1:5 is mixed by potassium methyl silicate, potassium silicate, polyvinyl alcohol, then in mass ratio
The oxalic acid solution that mass concentration is 15% is added dropwise, the pH for adjusting mixed system is 4, obtains the thick solution of silica；
Step 2: the thick solution of the silica is subjected to centrifugation purification with 6000rpm, part salt is removed, grain is then added
The simple substance nano silica fume that diameter is 30nm-80nm is mixed, while it is that 15% ammonia spirit adjusts mixed system that mass concentration, which is added dropwise,
PH be 7, then carry out ultrasonic disperse, obtain a nanometer elementary silicon/silica mixed sols presoma, wherein simple substance nanometer
The mass ratio of sodium methyl silicate in silicon powder and step 1 is 1:15；
Step 3: nanometer elementary silicon/silica mixed sols presoma is kept the temperature into 30min under the conditions of 70 DEG C, is obtained
Leather hard nanometer elementary silicon/silica mixed gel；
Step 4: polyurethane nano particle, unifor, the 2- propylene for being 0.01:7:0.5:0.04 by mass ratio
Amide groups -2- methyl propane sulfonic acid, perfluoroalkyl polyethers obtain foaming combination in the emulsified 40min of 2500rpm speed conditions
Object；
Step 5: the composition, foam is mixed with leather hard nanometer elementary silicon/silica obtained in step 3 and is coagulated
Glue by 1:90 mass ratio mix, 10min-15min is then stood under 0.8MPa-1.5MPa vacuum condition, then normal pressure,
Foamable at a temperature of 110 DEG C will have leather hard nanometer elementary silicon/silica flexible to mix by the gas that foaming generates
The network gap for closing gel struts completely, forms the more uniform aerosil microcellular structure of size, and make nano-silicon list
Matter is particle studded to fix in the micropore, while the volatile organic components in foaming agent slowly being volatilized exclusion, is received
Rice elementary silicon/aerosil.
Embodiment 4
Present embodiments provide a kind of nanometer of elementary silicon/aerosil preparation method comprising following steps:
Step 1: with water being that 1:0.5:0.1:5 is mixed by sodium methyl silicate, sodium metasilicate, polyvinyl alcohol, then in mass ratio
The citric acid solution that mass concentration is 15% is added dropwise, the pH for adjusting mixed system is 4, obtains the thick solution of silica；
Step 2: the thick solution of the silica is subjected to centrifugation purification with 6000rpm, part salt is removed, grain is then added
The simple substance nano silica fume that diameter is 30nm-80nm is mixed, while it is that 15% ammonia spirit adjusts mixed system that mass concentration, which is added dropwise,
PH be 7, then carry out ultrasonic disperse, obtain a nanometer elementary silicon/silica mixed sols presoma, wherein simple substance nanometer
The mass ratio of sodium methyl silicate in silicon powder and step 1 is 1:20；
Step 3: nanometer elementary silicon/silica mixed sols presoma is kept the temperature into 35min under the conditions of 60 DEG C, is obtained
Leather hard nanometer elementary silicon/silica mixed gel；
Step 4: by mass ratio being the polyurethane nano particle of 0.01:6:0.5:0.05, ammonium hydrogen carbonate, acrylamide, complete
Fluorine caproic acid ammonia obtains composition, foam in the emulsified 40min of 2500rpm speed conditions；
Step 5: the composition, foam is mixed with leather hard nanometer elementary silicon/silica obtained in step 3 and is coagulated
Glue by 1:95 mass ratio mix, 10min-15min is then stood under 0.8MPa-1.5MPa vacuum condition, then normal pressure,
Foamable at a temperature of 120 DEG C will have leather hard nanometer elementary silicon/silica flexible to mix by the gas that foaming generates
The network gap for closing gel struts completely, forms the more uniform aerosil microcellular structure of size, and make nano-silicon list
Matter is particle studded to fix in the micropore, while the volatile organic components in foaming agent slowly being volatilized exclusion, is received
Rice elementary silicon/aerosil.
Embodiment 5
Present embodiments provide a kind of nanometer of elementary silicon/aerosil preparation method comprising following steps:
Step 1: with water in mass ratio it is that 1:1:0.1:7 is mixed by sodium methyl silicate, sodium metasilicate, polyvinyl alcohol, then drips
Adding mass concentration is 15% citric acid solution, and the pH for adjusting mixed system is 4, obtains the thick solution of silica；
Step 2: the thick solution of the silica is subjected to centrifugation purification with 6000rpm, part salt is removed, grain is then added
The simple substance nano silica fume that diameter is 30nm-80nm is mixed, while it is that 15% ammonia spirit adjusts mixed system that mass concentration, which is added dropwise,
PH be 7, then carry out ultrasonic disperse, obtain a nanometer elementary silicon/silica mixed sols presoma, wherein simple substance nanometer
The mass ratio of sodium methyl silicate in silicon powder and step 1 is 1:20；
Step 3: nanometer elementary silicon/silica mixed sols presoma is kept the temperature into 20min under the conditions of 80 DEG C, is obtained
Leather hard nanometer elementary silicon/silica mixed gel；
Step 4: polyurethane nano particle, benzene sulfonyl hydrazide, the 2- acrylamide for being 0.01:6:0.5:0.02 by mass ratio
Base -2- methyl propane sulfonic acid, perfluoroalkyl polyoxyethylene ether obtain foaming combination in the emulsified 40min of 2000rpm speed conditions
Object；
Step 5: the composition, foam is mixed with leather hard nanometer elementary silicon/silica obtained in step 3 and is coagulated
Glue by 1:90 mass ratio mix, 10min-15min is then stood under 0.8MPa-1.5MPa vacuum condition, then normal pressure,
Foamable at a temperature of 120 DEG C will have leather hard nanometer elementary silicon/silica flexible to mix by the gas that foaming generates
The network gap for closing gel struts completely, forms the more uniform aerosil microcellular structure of size, and make nano-silicon list
Matter is particle studded to fix in the micropore, while the volatile organic components in foaming agent slowly being volatilized exclusion, is received
Rice elementary silicon/aerosil.
Nanometer elementary silicon/aerosil is made as the negative electrode material of lithium ion battery in the present embodiment, lithium is made
Ion battery, after lithium ion battery circulation after charge and discharge 500 times, capacity retention ratio 91%.
Claims (7)
1. a kind of preparation method of the silicon composite for cathode of lithium battery, it is characterised in that the following steps are included:
Step 1: being 1:(0.3-1 by organosilicate, inorganic silicate, polyvinyl alcohol and water in mass ratio): (0.1-0.2):
(3-7) mixing obtains the first mixture, and it is 3-6 that acid solution is added dropwise in the first mixture of Xiang Suoshu and adjusts its pH, obtains titanium dioxide
The thick solution of silicon；
Step 2: carrying out centrifugation purification for the thick solution of the silica, and simple substance nano silica fume is then added, obtains the second mixing
Object, it is 7-9 that Xiang Suoshu second, which mixes species and ammonia spirit is added dropwise to adjust its pH, then carries out ultrasonic disperse, obtains nano-silicon list
Matter/silica mixed sols presoma, wherein the mass ratio of the simple substance nano-silicon powder and the machine silicate is 1:
(5-20), the partial size of the nanometer elementary silicon are 30nm-80nm；
Step 3: the nanometer elementary silicon/silica mixed sols presoma is kept the temperature into 20min- under the conditions of 50 DEG C -80 DEG C
40min obtains leather hard nanometer elementary silicon/silica mixed gel；
Step 4: polyurethane nano particle, foaming agent, polymer emulsion, fluorocarbon surfactant are turned in 1500-2500rpm
The fast emulsified 30min-40min of condition, obtains composition, foam；
Step 5: the composition, foam is mixed with the leather hard nanometer elementary silicon/silica mixed gel, in vacuum
Under the conditions of stand 10min-15min, then foamable at a temperature of normal pressure, 100 DEG C -120 DEG C, obtains nanometer elementary silicon/bis-
Silica aerogel obtains the silicon composite for cathode of lithium battery through refinement classification；The composition, foam and described half
The mass ratio of dry shape nanometer elementary silicon/silica mixed gel is 1:(80-95).
2. a kind of preparation method of the silicon composite for cathode of lithium battery according to claim 1, it is characterised in that: institute
Stating organosilicate includes sodium methyl silicate or potassium methyl silicate；The inorganic silicate includes sodium metasilicate or potassium silicate.
3. a kind of preparation method of the silicon composite for cathode of lithium battery according to claim 1, it is characterised in that: institute
Stating acid solution is any one of hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, oxalic acid, acetic acid or citric acid.
4. a kind of preparation method of the silicon composite for cathode of lithium battery according to claim 1, it is characterised in that: institute
The mass concentration for stating acid solution is 5%-15%, and the mass concentration of the ammonia spirit is 5%-15%.
5. a kind of preparation method of the silicon composite for cathode of lithium battery according to claim 1, it is characterised in that: institute
Stating foaming agent includes azodicarbonamide, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, unifor, N, and N '-two is sub-
Any one of five methine tetramine of nitro, ammonium hydrogen carbonate；The polymer emulsion is acrylamide, potassium acrylate, 2- propylene
Any one of amide groups -2- methyl propane sulfonic acid；The fluorocarbon surfactant be N, N- dihydroxy ethyl perfluoroalkyl amide,
Any in perfluoro caprylic acid ammonia, perfluor caproic acid ammonia, perfluoroalkyl betain, perfluoroalkyl polyethers and perfluoroalkyl polyoxyethylene ether
Kind.
6. a kind of preparation method of the silicon composite for cathode of lithium battery according to claim 1, it is characterised in that: institute
State polyurethane nano particle, foaming agent, polymer emulsion, fluorocarbon surfactant mass ratio be 0.01:(5-8): (0.5-
1): (0.02-0.05).
7. a kind of silicon composite for cathode of lithium battery, it is characterised in that: by preparation described in any one of claims 1-6
The silicon composite for cathode of lithium battery that method is prepared, structure are that nanometer elementary silicon is embedded in silica airsetting
The three-dimensional net structure formed in the micropore of glue.
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| CN113013386A (en) * | 2019-12-19 | 2021-06-22 | 山西沃特海默新材料科技股份有限公司 | Composite negative electrode material and preparation method thereof |
| CN110975774B (en) * | 2019-12-25 | 2021-12-17 | 山东圣泉新材料股份有限公司 | Polymer microsphere and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555018A (en) * | 2009-05-15 | 2009-10-14 | 中国科学院广州能源研究所 | Method for preparing nano-porous materials with high mechanical property by organic modification |
| CN101973557A (en) * | 2010-11-05 | 2011-02-16 | 北京化工大学 | Method for preparing high-purity mono-disperse silicon dioxide hydrosol |
| CN104577049A (en) * | 2014-12-26 | 2015-04-29 | 中天科技精密材料有限公司 | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material |
| CN105621420A (en) * | 2015-12-23 | 2016-06-01 | 成都新柯力化工科技有限公司 | Method for preparing silicon dioxide aerogel through foaming |
-
2016
- 2016-11-04 CN CN201610960786.0A patent/CN106450208B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555018A (en) * | 2009-05-15 | 2009-10-14 | 中国科学院广州能源研究所 | Method for preparing nano-porous materials with high mechanical property by organic modification |
| CN101973557A (en) * | 2010-11-05 | 2011-02-16 | 北京化工大学 | Method for preparing high-purity mono-disperse silicon dioxide hydrosol |
| CN104577049A (en) * | 2014-12-26 | 2015-04-29 | 中天科技精密材料有限公司 | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material |
| CN105621420A (en) * | 2015-12-23 | 2016-06-01 | 成都新柯力化工科技有限公司 | Method for preparing silicon dioxide aerogel through foaming |
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