CN106711431A - Silicon-base cathode material for lithium ion battery and preparation method of silicon-base cathode material - Google Patents
Silicon-base cathode material for lithium ion battery and preparation method of silicon-base cathode material Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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Abstract
The invention relates to a silicon-base cathode material for a lithium ion battery and a preparation method of the silicon-base cathode material. The preparation method of the silicon-base cathode material comprises the steps that 1) nano silicon powder and hydrochloric acid are mixed, stirred at a room temperature, and then subjected to suction filtration to obtain surface-treated nano silicon powder; 2) a Tris solution is prepared; a dopamine monomer is added to the obtained Tris solution under a nitrogen supply condition; and sufficient stirring is performed to obtain a dopamine solution; and 3) the surface-treated nano silicon powder and the dopamine solution are mixed and sufficiently stirred under a vacuum condition; and then a polymerization reaction is performed in atmosphere to obtain the silicon-base cathode material. According to the method, the nano silicon powder is treated with concentrated hydrochloric acid, a silica oxidation layer is introduced on the surface of the nano silicon powder, and the mechanical strength of the oxidation layer is high, so that a buffer effect is exerted on expansion of the silicon powder. In addition, the silicon powder coating more complete polydopamine is obtained after hydrochloric acid treatment, and CMC (carboxy methylated cellulose) serving as a binding agent and the silicon-base cathode material are used cooperatively, so that the obtained lithium ion battery has better cycle efficiency and initial efficiency.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery silicon based anode material and its
Preparation method.
Background technology
With electronic apparatus miniaturization, energetic, portability develop, large-scale energy storage device, the development of space technology and
The development and exploitation of electric automobile, people are to performance of lithium ion battery requirement more and more higher, and performance of lithium ion battery such as compares
The improvement of capacity, cycle performance and high rate performance etc. depends primarily on carrying for embedding lithium electrode material energy densities and cycle life
It is high.The theoretical lithium storage content of the widely used graphite-like carbon based negative electrodes material of current lithium ion battery is relatively low, and its theoretical maximum is held
It is 372mAh/g to measure, it is clear that do not adapted to the demand of development, therefore exploitation novel high-performance negative material has turned into when business
It is anxious.
Silica-base material because with the theoretical embedding lithium capacity (4200mAh/g, far above other negative materials) of highest extremely
Attract attention.But silica-base material is under the conditions of high level removal lithium embedded, cubical expansivity is higher than 300%, and Volumetric expansion is serious, makes
Cyclical stability into battery significantly declines.The cycle performance for how improving silica-base material is a present research emphasis.
The content of the invention
The technical problems to be solved by the invention are directed to above shortcomings in the prior art, there is provided a kind of lithium ion
Battery silicon based anode material and preparation method thereof.
In order to solve the above technical problems, the technical scheme that the present invention is provided is:
A kind of lithium ion battery silicon based anode material is provided, the negative material has receiving for poly-dopamine for Surface coating
Rice silica flour, it is prepared by following methods:
1) nano silica fume is mixed with hydrochloric acid solution by mass volume ratio 0.1g/50~100mL, treatment is stirred at room temperature
0.5~1h, then suction filtration, washing are until filter liquor is neutrality, and the zeta current potentials of particle surface are negative electricity, are obtained at surface
The nano silica fume of reason;
2) trishydroxymethylaminomethane is dissolved in and Tris solution is obtained in deionized water, under logical condition of nitrogen gas, to gained
DOPA amine monomers are added in Tris solution, is sufficiently stirred for, and the pH value of solution is adjusted to 8.5 with hydrochloric acid solution, obtain dopamine
Solution;
3) under vacuum by step 1) nano silica fume and the step 2 of gained surface treatment) gained dopamine solution mixes
Close, wherein nano silica fume and the mass ratio of DOPA amine monomers in dopamine solution is 1:1.5-2.5, is sufficiently stirred for, and then removes
, there is polymerisation in vacuum, post processing obtains Surface coating the nano silica fume of poly-dopamine, i.e. lithium ion under air atmosphere
Battery silicon based anode material.
By such scheme, step 1) the nano silica fume particle diameter be 100-120nm;Step 1) and step 2) hydrochloric acid is molten
Liquid is that concentration is the concentrated hydrochloric acid of 37wt%.
By such scheme, step 2) the Tris solution concentrations be 10~50mM, dopamine in the dopamine solution
Concentration is 1.5-2.5g/L.
By such scheme, step 3) time of the polymerisation is 12~24h, the post processing includes deionization washing
Wash, suction filtration, vacuum drying.
The present invention also provides the preparation method of above-mentioned lithium ion battery silicon based anode material, and its step is as follows:
1) nano silica fume is mixed with hydrochloric acid solution by mass volume ratio 0.1g/50~100mL, treatment is stirred at room temperature
0.5~1h, then suction filtration, washing are until filter liquor is neutrality, and the zeta current potentials of particle surface are negative electricity, are obtained at surface
The nano silica fume of reason;
2) trishydroxymethylaminomethane is dissolved in and Tris solution is obtained in deionized water, under logical condition of nitrogen gas, to gained
DOPA amine monomers are added in Tris solution, is sufficiently stirred for, and the pH value of solution is adjusted to 8.5 with hydrochloric acid solution, obtain dopamine
Solution;
3) under vacuum by step 1) nano silica fume and the step 2 of gained surface treatment) gained dopamine solution mixes
Close, wherein nano silica fume and the mass ratio of DOPA amine monomers in dopamine solution is 1:1.5-2.5, is sufficiently stirred for, and then removes
, there is polymerisation in vacuum, post processing obtains Surface coating the nano silica fume of poly-dopamine, i.e. lithium ion under air atmosphere
Battery silicon based anode material.
And the lithium ion battery prepared according to above-mentioned silicon based anode material, it is made using CMC as binding agent with water
For solvent prepares lithium ion battery.
The present invention also provides the preparation method of above-mentioned lithium ion battery, and its step is as follows:
1) CMC is first dissolved with deionized water, magnetic agitation is to obtaining homogeneous phase solution;
2) by silicon based anode material and acetylene black mixed grinding half an hour, pour into step 1) gained homogeneous phase solution in, be added dropwise
Tween20 solution, magnetic agitation obtains slurry;
3) slurry is applied on a current collector with predetermined thickness, vacuum drying, compressing tablet form GND;
4) by step 3) gained GND based on assembling obtain lithium ion battery.
By such scheme, the mass ratio of the silicon based anode material, acetylene black and CMC is 4-20:3-4:2.
The application processes nano-silicon with hydrochloric acid, and layer of silicon dioxide layer is introduced in silicon powder surface, increases nano silica fume
Hydrophily, is easy to coating modification, and on the other hand, the mechanical performance of silicon dioxide layer is very strong, it is allowed to which lithium ion passes through, and in lithium
Suppress the expansion of silicon when ion passes through to a certain extent.
Coating modification for poly-dopamine to nano silica fume:Near pH value 8.5, in nitrogen atmosphere, DOPA amine monomers
First it is completely dissolved in Tris solution, due to having isolated oxidant oxygen, this process is simple dissolving, then by matrix material
Nano silica fume after surface treatment is placed in there-necked flask, and dopamine solution is placed in reaction bulb, carries out logical N2Protection, excludes reaction
Air in bottle, then by dopamine solution be quickly adding into it is another be connected in the constant pressure of there-necked flask titration funnel, taking out true
Under conditions of sky, the air in emptying system is in certain negative pressure state in system, opens the cock of reaction bulb, constant pressure drop
Determine during the dopamine solution in funnel slowly drops to there-necked flask, and slow three hours of magnetic agitation under vacuumized conditions, make
DOPA amine monomers are sufficiently mixed with matrix material nano silica fume, then open bottle stopper and be connected with air, oxidation occur poly- in there-necked flask
Reaction is closed, subsequent suction filtration obtains coating the nano-silicon of more complete poly-dopamine cladding.
During using aqueous binders CMC, electrode slice surface tension is excessive, and slurry is difficult to be bonded on Copper Foil, and occurs " to rise
Skin " phenomenon, so slurry will apply very thin, it is impossible to by electrode slice roll, fold, adds hydroaropic substance, a few drop 2.5wt%'s
Tween20, increases caking property of the slurry on Copper Foil, using CMC as binding agent, can improve acetylene black in the slurry point
Dissipate property.
For the bulk effect of silicon, the present invention coats nano-silicon with poly-dopamine, acetylene black in raising electrode system
Content, using CMC as binding agent, with water as solvent, forms more stable electrode, and buffer volumes bulking effect is effectively carried
The stability of silicon based anode material high.The present invention uses CMC (carboxymethylcellulose calcium) as binding agent, the carboxyl-functional of CMC
Group is stronger with the adhesion of silicon, so that the stability of electrode is significantly improved, while promoting SEI film (solid electrolyte interfaces
Film) formation, CMC is a kind of very crisp binding agent, and 5%~8% can only be extended before fracture, and considers the body of silicon in cyclic process
Product change reaches 300%, CMC binding agents can be ruptured in cyclic process, and it is steady more preferable charge and discharge cycles occur using CMC
Qualitative, reason is the structure that is stretched in aqueous solvent of carboxymethylcellulose calcium to the shape for being conducive to active particle and conductive network structure
Into, and nano-silicon occurs structure destruction, efflorescence, the reunion caused because embedding lithium causes volumetric expansion in charge and discharge process
And cause the problem of the rapid decay of capacity.By introducing one layer of polymeric layer, and nano-silicon is effectively wrapped up with unformed PDA layers
Get up with isolation, therefore, prepared composite makees electrode material, and capacity is high, steady with excellent structural stability, circulation
Qualitative and high rate performance.
The beneficial effects of the present invention are:Present invention concentrated hydrochloric acid oxidation processes nano silica fume, draws on nano silica fume surface
Enter layer of silicon dioxide oxide layer, silica oxide layer has mechanical strength very high, to a certain extent to nano silica fume
Expansion play cushioning effect, in addition, after HCl treatment, nano silica fume is easier to be sufficiently mixed with dopamine solution so that
Obtain coating the more complete silica flour of poly-dopamine, the use of water is solvent using CMC (carboxymethylcellulose calcium) as binding agent, with
Silicon based anode material prepared by the present invention is used cooperatively, and gained lithium ion battery has more preferable cycle efficieny and starting efficiency,
Embodiment 1, it is 72.46% that battery first circle coulombic efficiency is obtained, and battery first circle coulombic efficiency is obtained in pure nano-silicon
68.95%, because the poly-dopamine on nano silica fume surface contains great amount of hydroxy group, can further key with the carboxyl of binding agent
Knot, forms overall stabilized electrodes, and the structure that carboxymethylcellulose calcium stretches in aqueous solvent is to being also beneficial to active particle and conduction
The formation of network structure.
Brief description of the drawings
Fig. 1 is the Raman spectrum of the powder, pure nano silica fume and poly-dopamine PDA prepared by the embodiment of the present invention 1
(wherein 1 is pure nano silica fume Raman spectrum to figure, and 2 is the Raman spectrum of polymer P DA powder, and 3 is powder prepared by embodiment 1
The Raman spectrogram at end);
Fig. 2 is the SEM photograph of pure nano silica fume;
Fig. 3 is the SEM photograph of the reactive powder prepared by embodiment 1;
Fig. 4 is the TEM photos of the reactive powder prepared by embodiment 1;
Negative material the following in 200mA/g of silicon based anode materials and pure nano silica fume of the Fig. 5 prepared by embodiment 1
Ring performance photo;
Fig. 6 is cycle performance photo of the silicon based anode material prepared by embodiment 1 in 200mA/g;
Multiplying power of silicon based anode materials of the Fig. 7 prepared by embodiment 1 and pure nano silica fume under different current densities
Performance photo.
Specific embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
A kind of lithium ion battery silicon based anode material, its preparation process is as follows:
1) 0.1g nano silica fumes (particle diameter is 100-120nm) are mixed with the concentrated hydrochloric acid that 90mL concentration is 37wt%, in room
The lower magnetic agitation treatment 1h of temperature, then suction filtration, washing are until filter liquor is neutrality, and the zeta current potentials of particle surface are negative
Electricity, the nano silica fume being surface-treated;
2) 0.1211g trishydroxymethylaminomethanes are added in the beaker equipped with 100mL deionized waters, prepare Tris molten
Liquid, under logical condition of nitrogen gas, to 0.2g DOPA amine monomers are added in gained Tris solution, is sufficiently stirred for, and obtains dopamine solution,
With the pH value of pH test paper test solutions, and with the pH value of the hydrochloric acid conditioning solution of 37wt% to 8.5;
3) by step 2) gained dopamine mixed solution be quickly poured into constant pressure titration funnel in, air-isolation is being vacuumized
Under conditions of, make in system in certain negative pressure state, the cock that constant pressure titrates funnel is opened, it is many in constant pressure titration funnel
Bar amine aqueous solution slowly drips, with step 1) gained surface treatment nano silica fume mix, continuation under vacuumized conditions slow magnetic
Power stirs three hours, makes DOPA amine monomers be sufficiently mixed with matrix material nano silica fume, then open bottle stopper to be connected with air,
There is polymerisation under air atmosphere, reaction solution is washed with deionized after reaction 24h, suction filtration, until filter liquor is close to saturating
It is bright, then be vacuum dried and obtain Surface coating and have the nano silica fume of poly-dopamine, i.e. lithium ion battery silicon-based anode reactive powder.
Lithium ion battery is prepared based on above-mentioned gained silicon based anode material, is comprised the following steps that:
A) CMC, wherein CMC 17.5mg are first dissolved with deionized water, deionized water used makes solution reach conjunction to add
Suitable viscosity is advisable, and magnetic agitation 10 hours is to obtaining homogeneous phase solution;
B) by 35mg silicon-based active materials manufactured in the present embodiment and 35mg acetylene black mixed grinding half an hour, step is poured into
A) in gained homogeneous phase solution, wherein the mass ratio of the silicon based anode material, acetylene black and CMC is 4:4:2,2.5wt% is added dropwise
Tween20 solution 3 drip, magnetic agitation obtains slurry in 10 hours;
C) slurry is coated on collector (Copper Foil) for 90 microns with predetermined thickness, vacuum drying, compressing tablet form electricity at 80 DEG C
Pond negative pole;
D) based on step c) gained GNDs, metal lithium sheet is used for electrode, electrolyte is 1mol/L
LiPF6(volume ratio is 1 to/EC-DMC:1), polypropylene micropore diaphragm is barrier film (Celgard2300), and assembling obtains lithium-ion electric
Pond.
It is as shown in Figure 1 the Raman spectrogram of the silicon-based anode reactive powder prepared by the embodiment of the present invention, curve 1,2,3
Be respectively pure nano silica fume, PDA polymer (trishydroxymethylaminomethane for taking 0.1211g is added in the beaker of 100mL,
Add the Dopamine hydrochloride powder of 0.2g, be placed in magnetic agitation in air, react 24 hours, after the completion of reaction, spend from
Sub- water washing, suction filtration for several times, are vacuum dried at 60 DEG C of the powder for obtaining, you can be obtained) and Surface coating manufactured in the present embodiment
There is the Raman spectrogram of the nano silica fume of poly-dopamine, the characteristic absorption peak that it contains silica flour and PDA as shown in Figure 1, in Raman
Spectrally, silicon-based anode reactive powder PDA manufactured in the present embodiment coats nano-silicon powder (PDA@Si) and shows and poly- DOPA
Peak position wide, 1580cm as amine-1And 1470cm-1, from the bending stretching vibration of phenyl ring, Fig. 2 is pure nano silica fume
SEM photograph, Fig. 3 and 4 be respectively the present embodiment prepared by silicon-based anode reactive powder SEM photograph and TEM photos, can see
The silicon powder surface gone out after coated polymer becomes coarse, illustrates that PDA has successfully been coated on nano silica fume surface.
Fig. 5 is the cycle performance photo of silicon-based anode reactive powder manufactured in the present embodiment and pure silica flour in 200mA/g,
It can be seen that, compared with pure silica flour, the cyclical stability of silicon-based anode active powder material manufactured in the present embodiment is obviously improved, figure
6 is silicon based anode material obtained in the present embodiment in 200mA/g by the cycle performance photo under 310 cycling conditions, is passed through
310 specific discharge capacities of cycle battery are 1087.5mAh/g, and the capacity of later stage battery is gradually increasing, and is followed with good
Ring stability.
Fig. 7 be silicon-based anode reactive powder manufactured in the present embodiment and pure nano silica fume under different current densities times
Rate performance photo, curve 1 is the curve of double curvature of the battery for originally applying example preparation, the battery that curve 2 is prepared for pure nano-silicon times
Rate curve, as seen from the figure, the combination electrode material has good high rate performance, even if experience high current density discharge and recharge, extensive
When arriving low current density again, its specific discharge capacity can recover substantially, and with specific discharge capacity 1819.6mAh/g higher.
Embodiment 2
Lithium ion battery silicon based anode material is prepared using method similar to Example 1, difference is, step
1) with concentrated hydrochloric acid process nano silica fume time be 0.5h, step 2) Tris solution by 0.6g trishydroxymethylaminomethanes with
100mL deionized water mixed preparings are obtained.
After tested, silicon based anode material manufactured in the present embodiment is approached with the gained silicon based anode material performance of embodiment 1.
Embodiment 3
Lithium ion battery silicon based anode material is prepared using method similar to Example 1, difference is, step
1) it is 60mL with concentrated hydrochloric acid volume.
Above-mentioned gained silicon-based anode powder prepares lithium ion battery, comprises the following steps that:
A) CMC, wherein CMC 3.5mg are first dissolved with deionized water, deionized water used makes solution reach conjunction to add
Suitable viscosity is advisable, and magnetic agitation 10 hours is to obtaining homogeneous phase solution;
B) by silicon-based active material 35mg manufactured in the present embodiment and acetylene black 5.25mg mixed grinding half an hour, before pouring into
In the step gained homogeneous phase solution of face, the mass ratio of so wherein described silicon based anode material, acetylene black and CMC is 80:12:8, drop
Plus the Tween20 solution 3 of 2.5wt% drips, magnetic agitation obtains slurry in 10 hours;
C) slurry is coated on collector (Copper Foil) for 90 microns with predetermined thickness, vacuum drying, compressing tablet form electricity at 80 DEG C
Pond negative pole;
D) based on step c) gained GNDs, metal lithium sheet is used for electrode, electrolyte is 1mol/L
LiPF6(volume ratio is 1 to/EC-DMC:1), polypropylene micropore diaphragm is barrier film (Celgard2300), and assembling obtains lithium-ion electric
Pond.
After tested, silicon based anode material manufactured in the present embodiment and lithium ion battery connect with the products obtained therefrom performance of embodiment 1
Closely.
Embodiment 4
A kind of lithium ion battery silicon based anode material, its preparation process is as follows:
1) 0.1g nano silica fumes (particle diameter is 100-120nm) are mixed with the concentrated hydrochloric acid that 90mL concentration is 37wt%, in room
The lower magnetic agitation treatment 0.5h of temperature, then suction filtration, washing are until filter liquor is neutrality, and the zeta current potentials of particle surface are negative
Electricity, the nano silica fume being surface-treated;
2) 0.6g trishydroxymethylaminomethanes are added in the beaker equipped with 100mL deionized waters, prepare Tris solution,
Under logical condition of nitrogen gas, to 0.15g DOPA amine monomers are added in gained Tris solution, it is sufficiently stirred for, obtains dopamine solution, uses
The pH value of pH test paper test solutions, and with the pH value of the hydrochloric acid conditioning solution of 37wt% to 8.5;
3) by step 2) gained dopamine mixed solution be quickly poured into constant pressure titration funnel in, air-isolation is being vacuumized
Under conditions of, make in system in certain negative pressure state, the cock that constant pressure titrates funnel is opened, it is many in constant pressure titration funnel
Bar amine aqueous solution slowly drips, with step 1) gained surface treatment nano silica fume mix, continuation under vacuumized conditions slow magnetic
Power stirs three hours, makes DOPA amine monomers be sufficiently mixed with matrix material nano silica fume, then open bottle stopper to be connected with air,
There is polymerisation under air atmosphere, reaction solution is washed with deionized after reaction 18h, suction filtration, until filter liquor is close to saturating
It is bright, then be vacuum dried and obtain Surface coating and have the nano silica fume of poly-dopamine, i.e. lithium ion battery silicon-based anode reactive powder.
Above-mentioned gained silicon-based anode powder prepares lithium ion battery, comprises the following steps that:
A) CMC, wherein CMC 17.5mg are first dissolved with deionized water, deionized water used makes solution reach conjunction to add
Suitable viscosity is advisable, and magnetic agitation 10 hours is to obtaining homogeneous phase solution;
B) by silicon-based active material 35mg manufactured in the present embodiment and acetylene black 35mg mixed grinding half an hour, step is poured into
A) in gained homogeneous phase solution, the mass ratio of the silicon based anode material, acetylene black and CMC is 4:4:2, it is added dropwise 2.5wt%'s
Tween20 solution 3 drips, and magnetic agitation obtains slurry in 10 hours;
C) slurry is coated on collector (Copper Foil) for 90 microns with predetermined thickness, vacuum drying, compressing tablet form electricity at 80 DEG C
Pond negative pole;
D) based on step c) gained GNDs, metal lithium sheet is used for electrode, electrolyte is 1mol/L
LiPF6(volume ratio is 1 to/EC-DMC:1), polypropylene micropore diaphragm is barrier film (Celgard2300), and assembling obtains lithium-ion electric
Pond.
After tested, silicon based anode material manufactured in the present embodiment and lithium ion battery connect with the products obtained therefrom performance of embodiment 1
Closely.
Embodiment 5
A kind of lithium ion battery silicon based anode material, its preparation process is as follows:
1) 0.1g nano silica fumes (particle diameter is 100-120nm) are mixed with the concentrated hydrochloric acid that 50mL concentration is 37wt%, in room
The lower magnetic agitation treatment 1h of temperature, then suction filtration, washing are until filter liquor is neutrality, and the zeta current potentials of particle surface are negative
Electricity, the nano silica fume being surface-treated;
2) 0.6g trishydroxymethylaminomethanes are added in the beaker equipped with 80mL deionized waters, prepare Tris solution,
Under logical condition of nitrogen gas, to 0.25g DOPA amine monomers are added in gained Tris solution, it is sufficiently stirred for, obtains dopamine solution, uses
The pH value of pH test paper test solutions, and with the pH value of the hydrochloric acid conditioning solution of 37wt% to 8.5;
3) by step 2) gained dopamine mixed solution be quickly poured into constant pressure titration funnel in, air-isolation is being vacuumized
Under conditions of, make in system in certain negative pressure state, the cock that constant pressure titrates funnel is opened, it is many in constant pressure titration funnel
Bar amine aqueous solution slowly drips, with step 1) gained surface treatment nano silica fume mix, continuation under vacuumized conditions slow magnetic
Power stirs three hours, makes DOPA amine monomers be sufficiently mixed with matrix material nano silica fume, then open bottle stopper to be connected with air,
There is polymerisation under air atmosphere, reaction solution is washed with deionized after reaction 12h, suction filtration, until filter liquor is close to saturating
It is bright, then be vacuum dried and obtain Surface coating and have the nano silica fume of poly-dopamine, i.e. lithium ion battery silicon-based anode reactive powder.
Above-mentioned gained silicon-based anode powder prepares lithium ion battery, comprises the following steps that:
A) CMC, wherein CMC 17.5mg are first dissolved with deionized water, deionized water used makes solution reach conjunction to add
Suitable viscosity is advisable, and magnetic agitation 10 hours is to obtaining homogeneous phase solution;
B) by silicon-based active material 35mg manufactured in the present embodiment and acetylene black 35mg mixed grinding half an hour, step is poured into
A) in gained homogeneous phase solution, the mass ratio of the silicon based anode material, acetylene black and CMC is 4:4:2, it is added dropwise 2.5wt%'s
Tween20 solution 3 drips, and magnetic agitation obtains slurry in 10 hours;
C) slurry is coated on collector (Copper Foil) for 90 microns with predetermined thickness, vacuum drying, compressing tablet form electricity at 80 DEG C
Pond negative pole;
D) based on step c) gained GNDs, metal lithium sheet is used for electrode, electrolyte is 1mol/L
LiPF6(volume ratio is 1 to/EC-DMC:1), polypropylene micropore diaphragm is barrier film (Celgard2300), and assembling obtains lithium-ion electric
Pond.
After tested, silicon based anode material manufactured in the present embodiment and lithium ion battery connect with the products obtained therefrom performance of embodiment 1
Closely.
Claims (8)
1. a kind of lithium ion battery silicon based anode material, it is characterised in that the negative material poly- DOPA for Surface coating has
The nano silica fume of amine, it is prepared by following methods:
1) nano silica fume is mixed with hydrochloric acid solution by mass volume ratio 0.1g/50~100mL, treatment 0.5 is stirred at room temperature
~1h, then suction filtration, washing are until filter liquor is neutrality, and the zeta current potentials of particle surface are negative electricity, are surface-treated
Nano silica fume;
2) trishydroxymethylaminomethane is dissolved in and Tris solution is obtained in deionized water, under logical condition of nitrogen gas, to gained Tris
DOPA amine monomers are added in solution, is sufficiently stirred for, and the pH value of solution is adjusted to 8.5 with hydrochloric acid solution, obtain dopamine solution;
3) under vacuum by step 1) nano silica fume and the step 2 of gained surface treatment) obtained by dopamine solution mix, its
Middle nano silica fume is 1 with the mass ratio of DOPA amine monomers in dopamine solution:1.5-2.5, is sufficiently stirred for, and then removes vacuum,
There is polymerisation under air atmosphere, post processing obtains Surface coating the nano silica fume of poly-dopamine, i.e. lithium ion battery
Use silicon based anode material.
2. lithium ion battery silicon based anode material according to claim 1, it is characterised in that:Step 1) nano-silicon
Powder footpath is 100-120nm;Step 1) and step 2) hydrochloric acid solution be concentration for 37wt% concentrated hydrochloric acid.
3. lithium ion battery silicon based anode material according to claim 1, it is characterised in that:Step 2) Tris is molten
Liquid concentration is 10~50mM, and the concentration of dopamine is 1.5-2.5g/L in the dopamine solution.
4. lithium ion battery silicon based anode material according to claim 1, it is characterised in that:Step 3) polymerization is instead
The time answered is 12~24h, and the post processing includes deionized water washing, suction filtration, vacuum drying.
5. a kind of preparation method according to any described lithium ion battery silicon based anode materials of claim 1-4, its feature
It is step as follows:
1) nano silica fume is mixed with hydrochloric acid solution by mass volume ratio 0.1g/50~100mL, treatment 0.5 is stirred at room temperature
~1h, then suction filtration, washing are until filter liquor is neutrality, and the zeta current potentials of particle surface are negative electricity, are surface-treated
Nano silica fume;
2) trishydroxymethylaminomethane is dissolved in and Tris solution is obtained in deionized water, under logical condition of nitrogen gas, to gained Tris
DOPA amine monomers are added in solution, is sufficiently stirred for, and the pH value of solution is adjusted to 8.5 with hydrochloric acid solution, obtain dopamine solution;
3) under vacuum by step 1) nano silica fume and the step 2 of gained surface treatment) obtained by dopamine solution mix, its
Middle nano silica fume is 1 with the mass ratio of DOPA amine monomers in dopamine solution:1.5-2.5, is sufficiently stirred for, and then removes vacuum,
There is polymerisation under air atmosphere, post processing obtains Surface coating the nano silica fume of poly-dopamine, i.e. lithium ion battery
Use silicon based anode material.
6. a kind of lithium ion battery prepared with any described silicon based anode materials of claim 1-4, it is characterised in that:
Using CMC as binding agent, lithium ion battery is prepared as solvent using water.
7. the preparation method of the lithium ion battery described in a kind of claim 6, it is characterised in that step is as follows:
1) CMC is first dissolved with deionized water, magnetic agitation is to obtaining homogeneous phase solution;
2) by silicon based anode material and acetylene black mixed grinding half an hour, pour into step 1) gained homogeneous phase solution in, be added dropwise
Tween20 solution, magnetic agitation obtains slurry;
3) slurry is applied on a current collector with predetermined thickness, vacuum drying, compressing tablet form GND;
4) by step 3) gained GND based on assembling obtain lithium ion battery.
8. preparation method according to claim 7, it is characterised in that the matter of the silicon based anode material, acetylene black and CMC
Amount is than being 4-20:3-4:2.
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