Lithium battery silicon based anode material and preparation method thereof
Technical field
The present invention relates to lithium cell cathode material technical field, specially a kind of lithium battery silicon based anode material and its system
Preparation Method.
Background technique
It by lithium metal or lithium alloy is negative electrode material, using the battery of non-aqueous electrolytic solution that lithium battery, which is a kind of,;Lithium electricity
Pond is broadly divided into two classes: lithium metal battery and lithium ion battery.
Compared with conventional graphite material is as lithium ion battery negative material, silicon has the theoretical specific capacity of superelevation and lower
De- lithium current potential, and the voltage platform of silicon is slightly above graphite, analysis lithium in surface is not easy to cause in charging, security performance is more preferable, institute
With silica-base material becomes one of the potential selection of richness of the carbon-based cathode upgrading of lithium ion battery.
But silicon also has disadvantage as lithium ion battery negative material.Firstly, silicon is semiconductor material, the conductivity of itself
It is lower;Secondly, the insertion and abjection of lithium ion can make the expansion of 300% or more material volume generation in electrochemistry cyclic process
With contraction, the mechanicals efforts of generation can make material gradually dusting, cause structure collapses, eventually lead to electrode active material and collection
Fluid is detached from, and loses electrical contact, cycle performance of battery is caused to substantially reduce.Further, since this bulk effect, silicon is in electrolyte
In be difficult to form stable solid electrolyte interface film, with the destruction of electrode structure, in the continuous shape of silicon face exposed
The stationary electrolyte interfacial film of Cheng Xin exacerbates corrosion and the capacity attenuation of silicon.
In order to improve silicon-based anode cycle performance, structural stability of the material in cyclic process is improved, usually by silicon material
Expect nanosizing and Composite.
Wherein, nano silicon particles and three-dimensional porous structure silicon can inhibit the bulk effect of material to a certain extent,
The diffusion length of lithium ion can also be reduced simultaneously, improve electrochemical reaction speed.But their specific surface area is all very big, increases
With directly contacting for electrolyte, causes side reaction and irreversible capacity to increase, reduce coulombic efficiency.In addition, silicon active particle exists
It is easy to reunite in charge and discharge process, occur " electrochemistry sintering ", accelerate capacity attenuation.
Silicon nanowires/pipe can reduce volume change radial in charge and discharge process, realize good cyclical stability, and
It is axial that the quick transmission channel of lithium ion is provided.But the tap density that can reduce silicon materials leads to the volume and capacity ratio of silicium cathode
It reduces.Silicon thin film, which can be reduced, maintains the structural intergrity of electrode with film normal direction, the volume change of upper generation.But through more
After secondary circulation, silicon thin film easily occurs to be crushed, and is detached from substrate, and the preparation cost of silicon thin film is higher.
The electronic conductance of material can be improved in metal component during silicon/metal mold is compound, reduces the polarization of silicon materials, improves
The high rate performance of silicon materials.The ductility of metal can inhibit the bulk effect of silicon materials to a certain extent, improve cyclicity
Can, but silicon structure defect produced during the preparation process has very high electro-chemical activity, will lead to irreversible capacity and becomes larger.And silicon
It not can avoid activated silica with metal composite directly to contact with electrolyte, generate unstable SEI film, cycle performance of battery is caused to drop
It is low.
During silicon/carbon type is compound, because of carbon material electronic conductance with higher and ionic conductance, times of silica-base material can be improved
Rate performance inhibits bulk effect of the silicon in cyclic process.It directly contacts, reduces with electrolyte in addition, carbon material can obstruct silicon
Irreversible capacity.But the disadvantage is that the interfacial contact of both silicon materials and carbon material is poor, to the hole inner wall of silicon materials nanoscale
It is larger to carry out complete uniform carbon coating difficulty.
Nanosizing and Composite method are combined, porous silicon/carbon composite material is prepared, porous structure therein can have
Buffer volumes expansion is imitated, is reunited in cyclic process with the compound avoidable nano particle of carbon material, starting efficiency, circulation are improved
Stability and high rate performance.
Patent announcement number is that the patent of invention of CN105261733A discloses a kind of preparation of nano silicon-based/carbon composite
Method coats microporous carbonaceous layer in nanometer silicon face in liquid phase using organic resin and pore creating material first first, and then using hair
Ferment starch is coated, high temperature cabonization preparation as carbon source.It can be prepared using the method for the present invention special in the structure of " pomegranate " type
Nano silicon-based/carbon composite is levied, when being applied to production lithium ion battery negative material, can effectively solve body in process of intercalation
Particle Breakage, dusting in long-pending sharply expansion and cyclic process, the problem of falling off, the specific capacity of material is up to 450-950mAh/g,
Capacity retention ratio is 85-92% after cycle charge-discharge 500 weeks.But in above-mentioned technical proposal pomegranate type structure feature nano-silicon
Base/carbon composite can reduce the tap density of material itself, and the volume and capacity ratio of cathode is caused to reduce, so as to cause can not be real
The technical issues of now further increasing the reversible specific capacity and cycle performance of lithium ion battery.
The present invention provides a kind of lithium battery silicon based anode material and preparation method thereof, it is intended to solve nano silica-base material with
Carbon material, since the tap density of nano silicon-based/carbon negative pole material itself reduces, causes when being combined pomegranate type structure
The technical issues of volume and capacity ratio of negative electrode of lithium ion battery reduces.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of lithium battery silicon based anode materials and preparation method thereof, solve
Nano silica-base material and carbon material, when being combined pomegranate type structure, due to the vibration of nano silicon-based/carbon negative pole material itself
The technical issues of real density reduces, and leading to the volume and capacity ratio of negative electrode of lithium ion battery reduces.
(2) technical solution
To achieve the above object, the invention provides the following technical scheme:
Lithium battery silicon based anode material, including silicon source material and carbon source material, the silicon source material are combined into carbon source material
In the close covering body of pomegranate type structure, and carbon source coats silicon source, and silicon source is tightly distributed in the gap of carbon source;
The silicon source include partial size be 10-50um polycrystalline silicon powder, partial size be 100-500nm crystalline silicon, partial size 10-50nm
Crystalline silicon;
The silicon source such as includes at the graphite of mass parts and the mixture of graphene;
Circulation 500 times specific capacities of the silicon based anode material are 1214-1236mAh/g, the capacity retention ratio that circulation is 500 times
93.11-93.51%。
Preferably, the silicon source be partial size be 30um polycrystalline silicon powder, partial size be 200nm crystalline silicon, partial size 30nm
Crystalline silicon.
Preferably, the silicon source includes the raw material of following parts by weight: 2 parts of the polycrystalline silicon powder that partial size is 30um, partial size are
6 parts of the crystalline silicon of 200nm, 3 parts of crystalline silicon that partial size is 30nm.
Preferably, the circulation of the silicon based anode material 500 times specific capacities are 1236mAh/g, the capacity that circulation is 500 times
Conservation rate is 93.47%.
The preparation method of lithium battery silicon based anode material, comprising the following steps:
S1. by partial size be 10-50um polycrystalline silicon powder, partial size be 100-500nm crystalline silicon, partial size be 10-50nm crystal
Silicon is charged first to the hydrochloric acid and mass fraction that are 10-30% by mass fraction according to the proportion mode of mass ratio 1-3:5-7:2-5
Pickling 20-60min in the acid solution being formulated for the nitric acid of 5-20% according to the ratio of volume ratio 2:1;
It is then added to the deposition silver being made of the hydrofluoric acid that the silver nitrate solution and mass fraction of 0.02-0.06mol/L are 5-10%
In mixed solution, 20-60min is deposited, is rinsed well after the completion of deposition using deionized water, the silicon material of deposition silver is prepared
Material;
S2. the silicon materials prepared in step S1 are added to by the hydrofluoric acid of 8-10mol/L, the nitric acid that mass fraction is 5-10%
In the etchant solution that the hydrogen peroxide that solution and mass fraction are 15-20% forms, in the case where temperature is 40-60 DEG C, corrode 40-80min
Afterwards, it is rinsed well through deionized water, then drying and processing is carried out using infrared lamp, porous silica material is prepared;
S3. by the porous silica material prepared in step S2, graphite, graphene, polyvinyl alcohol, ultra-pure water solution, according to mass ratio
For 5-8:1-3:1-3:3-1:2-1 proportion mode carry out mixed preparing after, be placed in ball mill together, at 500r/min,
The silicon slurry of graphene coated is prepared in ball milling 3-5h;
S4. the silicon slurry of the graphene coated prepared in step S3 is applied on copper foil electrode collector, is placed in vacuum
In furnace, at 80-90 DEG C, the silicon materials electrode of graphene coated is prepared in dry 2-3h;
S5. the silicon materials electrode of the graphene coated prepared in step S4 is placed in vacuum drying oven, with the rate liter of 4-7 DEG C/min
Temperature arrives 850-950 DEG C, and at 850-950 DEG C, is sintered 40-60min, later, lithium battery is prepared in cooled to room temperature
Use silicon based anode material.
Preferably, in the step S3, porous silica material, graphite, graphene, polyvinyl alcohol, ultra-pure water solution, according to matter
Amount is than being that the proportion mode of 7:2:2:2:1 carries out mixed preparing.
Preferably, in the step S5, the silicon materials electrode of graphene coated is placed in vacuum drying oven, with the speed of 5 DEG C/min
Rate is warming up to 900 DEG C, and at 900 DEG C, is sintered 50min.
(3) beneficial effect
Compared with prior art, the present invention provides a kind of lithium battery silicon based anode material and preparation method thereof, have following
The utility model has the advantages that
1, silicon based anode material, by matching the crystalline silicon of the polycrystalline silicon powder of micron-level particle size Nano Particle different from two kinds
The mixing silicon source with level size composition is made, the mixing silicon source with can by the carbon source of the mass mixings such as graphite and graphene
It is combined into the close covering body in pomegranate type structure;
The lithium ion battery being made after tested by the silicon based anode material, the Average specific capacities that circulation is 500 times are 1214-
1236mAh/g, 500 capacity retention ratios are recycled as 93.11-93.51%, and the ratio of silicon based anode material in the prior art
Capacity 450-950mAh/g is improved significantly compared with capacity retention ratio 85-92% after circulation 500 weeks by pomegranate type structure
Close covering body composition silicon based anode material specific capacity and circulation volume conservation rate, dramatically increase nanometer to realize
Silicon substrate/carbon negative pole material tap density technical effect, and then obtain the volume and capacity ratio for significantly improving negative electrode of lithium ion battery
Technical effect.
2, the preparation method of the silicon based anode material, by first by the polycrystalline silicon powder of micron-level particle size nanometer different from two kinds
The crystalline silicon of grade partial size is configured to the mixing silicon source with level size composition, deposits silver in mixing silicon source, by deposition silver
Mixing silicon source is corroded, and porous silica material is prepared, then porous silica material and graphene, graphite are made to the silicon of graphene coated
Silicon slurry is then applied on copper foil electrode collector by slurry, and through dry with after sintering processes, silicon-based anode material is prepared
Material, the silicon based anode material which prepares, which not only realizes, dramatically increases nano silicon-based/carbon negative pole material vibration density
The technical effect of degree, and obtain the technical effect for significantly improving the volume and capacity ratio of negative electrode of lithium ion battery.
Specific embodiment
Embodiment one:
S1. by partial size be 10um polycrystalline silicon powder, partial size be 100nm crystalline silicon, partial size be 10nm crystalline silicon according to quality
Proportion mode than 1:5:2 is charged first to nitric acid that the hydrochloric acid and mass fraction that are 10% by mass fraction are 5% according to volume ratio
Pickling 20min in the acid solution that the ratio of 2:1 is formulated;
It is then added to the deposition silver mixed solution being made of the hydrofluoric acid that the silver nitrate solution and mass fraction of 0.02mol/L are 5%
In, 20min is deposited, is rinsed well after the completion of deposition using deionized water, the silicon materials of deposition silver are prepared;
S2. by the silicon materials prepared in step S1 be added to by the hydrofluoric acid of 8mol/L, the nitric acid solution that mass fraction is 5% and
In the etchant solution that the hydrogen peroxide that mass fraction is 15% forms, in the case where temperature is 40 DEG C, after corroding 40min, rushed through deionized water
Wash clean, then drying and processing is carried out using infrared lamp, porous silica material is prepared;
S3. by the porous silica material prepared in step S2, graphite, graphene, polyvinyl alcohol, ultra-pure water solution, according to mass ratio
For 5:1:1:3:2 proportion mode carry out mixed preparing after, be placed in ball mill together, at 500r/min, ball milling 3h, preparation
Obtain the silicon slurry of graphene coated;
S4. the silicon slurry of the graphene coated prepared in step S3 is applied on copper foil electrode collector, is placed in vacuum
In furnace, at 80 DEG C, the silicon materials electrode of graphene coated is prepared in dry 2h;
S5. the silicon materials electrode of the graphene coated prepared in step S4 is placed in vacuum drying oven, is heated up with the rate of 4 DEG C/min
To 850 DEG C, and at 850 DEG C, it is sintered 40min, later, lithium battery silicon-based anode material is prepared in cooled to room temperature
Material.
Embodiment two:
S1. by partial size be 30um polycrystalline silicon powder, partial size be 200nm crystalline silicon, partial size be 30nm crystalline silicon according to quality
Proportion mode than 2:6:3 is charged first to nitric acid that the hydrochloric acid and mass fraction that are 20% by mass fraction are 15% according to volume
Pickling 40min in the acid solution that ratio than 2:1 is formulated;
It is then added to the deposition silver mixed solution being made of the hydrofluoric acid that the silver nitrate solution and mass fraction of 0.04mol/L are 8%
In, 40min is deposited, is rinsed well after the completion of deposition using deionized water, the silicon materials of deposition silver are prepared;
S2. by the silicon materials prepared in step S1 be added to by the hydrofluoric acid of 9mol/L, the nitric acid solution that mass fraction is 8% and
In the etchant solution that the hydrogen peroxide that mass fraction is 18% forms, in the case where temperature is 50 DEG C, after corroding 60min, rushed through deionized water
Wash clean, then drying and processing is carried out using infrared lamp, porous silica material is prepared;
S3. by the porous silica material prepared in step S2, graphite, graphene, polyvinyl alcohol, ultra-pure water solution, according to mass ratio
For 7:2:2:2:1 proportion mode carry out mixed preparing after, be placed in ball mill together, at 500r/min, ball milling 3-5h, system
It is standby to obtain the silicon slurry of graphene coated;
S4. the silicon slurry of the graphene coated prepared in step S3 is applied on copper foil electrode collector, is placed in vacuum
In furnace, at 85 DEG C, the silicon materials electrode of graphene coated is prepared in dry 2.5h;
S5. the silicon materials electrode of the graphene coated prepared in step S4 is placed in vacuum drying oven, is heated up with the rate of 5 DEG C/min
To 900 DEG C, and at 900 DEG C, it is sintered 50min, later, lithium battery silicon-based anode material is prepared in cooled to room temperature
Material.
Embodiment three:
S1. by partial size be 50um polycrystalline silicon powder, partial size be 500nm crystalline silicon, partial size be 50nm crystalline silicon according to quality
Proportion mode than 3:7:5 is charged first to nitric acid that the hydrochloric acid and mass fraction that are 30% by mass fraction are 20% according to volume
Pickling 60min in the acid solution that ratio than 2:1 is formulated;
It is molten to be then added to the deposition silver mixing being made of the hydrofluoric acid that the silver nitrate solution and mass fraction of 0.06mol/L are 10%
In liquid, 60min is deposited, is rinsed well after the completion of deposition using deionized water, the silicon materials of deposition silver are prepared;
S2. the silicon materials prepared in step S1 are added to by the hydrofluoric acid of 10mol/L, the nitric acid solution that mass fraction is 10%
With mass fraction be 15-20% hydrogen peroxide form etchant solution in, temperature be 60 DEG C at, corrode 80min after, gone from
Sub- water is rinsed well, then carries out drying and processing using infrared lamp, and porous silica material is prepared;
S3. by the porous silica material prepared in step S2, graphite, graphene, polyvinyl alcohol, ultra-pure water solution, according to mass ratio
For 8:3:3:1:1 proportion mode carry out mixed preparing after, be placed in ball mill together, at 500r/min, ball milling 5h, preparation
Obtain the silicon slurry of graphene coated;
S4. the silicon slurry of the graphene coated prepared in step S3 is applied on copper foil electrode collector, is placed in vacuum
In furnace, at 90 DEG C, the silicon materials electrode of graphene coated is prepared in dry 3h;
S5. the silicon materials electrode of the graphene coated prepared in step S4 is placed in vacuum drying oven, is heated up with the rate of 7 DEG C/min
To 950 DEG C, and at 950 DEG C, it is sintered 60min, later, lithium battery silicon-based anode material is prepared in cooled to room temperature
Material.
Experimental example: the lithium ion battery being made by the silicon based anode material prepared in above-described embodiment, using lithium from
The electrochemical property test instrument of sub- battery tests Average specific capacities and the capacity holding that above-mentioned lithium ion battery carries out 500 circulations
Rate, test result are shown in Table 1.
Table 1
Embodiment | The Average specific capacities (mAh/g) that circulation is 500 times | The capacity retention ratio (%) that circulation is 500 times |
Embodiment one | 1214 | 93.11 |
Embodiment two | 1236 | 93.47 |
Embodiment three | 1231 | 93.51 |
Judgment criteria: in the prior art, the specific capacity of silicon based anode material is 450-950mAh/g, after cycle charge-discharge 500 weeks
Capacity retention ratio is 85-92%.
The beneficial effects of the present invention are: the lithium-ion electric being made by the silicon based anode material prepared in above-described embodiment
The circulation 500 times Average specific capacities in pond are 1214-1236mAh/g, the specific capacity with silicon based anode material in the prior art
450-950mAh/g is compared, and improves the specific capacity of silicon based anode material significantly, significantly improves lithium ion battery to realize
Reversible specific capacity technical effect;
Circulation 500 times capacity of the lithium ion battery being made by the silicon based anode material prepared in above-described embodiment are kept
Rate is 93.11-93.51%, compared with capacity retention ratio 85-92% behind circulation 500 weeks of silicon based anode material in the prior art,
The circulation volume conservation rate of silicon based anode material is improved significantly, to realize the cycle performance for significantly improving lithium ion battery
Technical effect.
Typical case: the crystalline substance that crystalline silicon that polycrystalline silicon powder that partial size is 30um by S1., partial size are 200nm, partial size are 30nm
For body silicon according to the proportion mode of mass ratio 2:6:3, being charged first to the hydrochloric acid and mass fraction that are 20% by mass fraction is 15%
Pickling 40min in the acid solution that nitric acid is formulated according to the ratio of volume ratio 2:1;
It is then added to the deposition silver mixed solution being made of the hydrofluoric acid that the silver nitrate solution and mass fraction of 0.04mol/L are 8%
In, 40min is deposited, is rinsed well after the completion of deposition using deionized water, the silicon materials of deposition silver are prepared;
S2. by the silicon materials prepared in step S1 be added to by the hydrofluoric acid of 9mol/L, the nitric acid solution that mass fraction is 8% and
In the etchant solution that the hydrogen peroxide that mass fraction is 18% forms, in the case where temperature is 50 DEG C, after corroding 60min, rushed through deionized water
Wash clean, then drying and processing is carried out using infrared lamp, porous silica material is prepared;
S3. by the porous silica material prepared in step S2, graphite, graphene, polyvinyl alcohol, ultra-pure water solution, according to mass ratio
For 7:2:2:2:1 proportion mode carry out mixed preparing after, be placed in ball mill together, at 500r/min, ball milling 3-5h, system
It is standby to obtain the silicon slurry of graphene coated;
S4. the silicon slurry of the graphene coated prepared in step S3 is applied on copper foil electrode collector, is placed in vacuum
In furnace, at 85 DEG C, the silicon materials electrode of graphene coated is prepared in dry 2.5h;
S5. the silicon materials electrode of the graphene coated prepared in step S4 is placed in vacuum drying oven, is heated up with the rate of 5 DEG C/min
To 900 DEG C, and at 900 DEG C, it is sintered 50min, later, lithium battery silicon-based anode material is prepared in cooled to room temperature
Circulation 500 times Average specific capacities of material, the lithium ion battery being made by the silicon based anode material are 1236mAh/g, follow
The capacity retention ratio that ring is 500 times is 93.47%.