CN105576221B - A kind of lithium ion battery anode active material presoma and lithium ion battery anode active material and preparation method thereof - Google Patents
A kind of lithium ion battery anode active material presoma and lithium ion battery anode active material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of lithium ion battery anode active material presoma and lithium ion battery anode active materials and preparation method thereof; the preparation method of the lithium ion battery anode active material includes mixing lithium ion battery anode active material presoma in organic solvent with graphite; then mixture is heated; it is evaporated organic solvent; then heat; reduction treatment is carried out after cooling under reducing atmosphere, carbonization treatment is finally carried out under protective atmosphere.Lithium ion battery anode active material is prepared using this method, graphite is evenly dispersed in preparation process, be not in caking phenomenon, do not need through subsequent ball-milling treatment, technique is more simple, and tin-cobalt alloy particle is coated on graphite surface with nanoscale, so that the negative electrode active material particle being prepared is uniform, the negative electrode material being prepared conducts electricity very well, and volume and capacity ratio is high, high rate performance is high, and cyclical stability is strong.
Description
Technical field
The present invention relates to a kind of lithium ion battery anode active material presoma and ion battery negative electrode active material and its
Preparation method, the lithium ion battery negative material formed by the lithium ion battery anode active material contain the lithium ion battery
The negative electrode of lithium ion battery of negative electrode material and lithium ion battery containing the negative electrode of lithium ion battery.
Background technique
With the high speed development of today's society Portable movable electronic equipment, to light-weight, small in size, capacity and energy
The market demand of the higher lithium ion battery of density is increasing.Lithium ion battery success application, key is can be reversible
The negative electrode material of ground insertion and deintercalate lithium ions, therefore, negative electrode material is the chief component of lithium ion battery, negative electrode material
Performance directly affect the performance of lithium ion battery.
Commercial Li-ion battery is all using carbon-based material as cathode, but due to the reversible capacity of graphite cathode at present
Only 372 mAh/g(LiC6), the development of the following lithium ion battery is seriously limited, therefore, there is an urgent need to one kind with higher
The lithium ion battery negative material of capacity.The study found that can form Sn, Co of alloy etc. with lithium has much higher than graphite cathode
Theoretical capacity.Therefore, the lithium-ion electric of high capacity is obtained by preparing the composite materials such as kamash alloy-graphite in the prior art
Pond negative electrode material, however, in the prior art, generalling use the method for step generation to prepare, such as CN200810203232.1 public affairs
A kind of tin-graphite composite negative pole material is opened, preparation method is used organic high score such as the organic solution of pink salt and pitch
Graphite is added after sub- mixed with polymers and is mixed to form gel/graphite mixed system, alkaline matter is added, heat drying is in high temperature
Under be heat-treated, obtain lithium ion battery anode active material；As CN200610020272.3 discloses a kind of lithium ion battery
Cathode tin carbon compound electrode material, mainly will by graphite material with mix up pink salt mixing after react in aqueous slkali,
Then it is coated with carbon source presoma and is carbonized to obtain；Above method is easy agglomeration after there is addition graphite, need to be through later
The grinding of phase, and the negative electrode active material particle being prepared is small, electric conductivity is poor.
Summary of the invention
The present invention solve the kamash alloy-graphite composite anode active material electric conductivity prepared in the prior art it is poor,
Graphite is easy the technical issues of agglomeration in preparation process, at the same provide a kind of new presoma, the presoma preparation method,
A kind of preparation method of lithium ion battery anode active material, the lithium ion battery anode active material being prepared by this method
And negative electrode of lithium ion battery.
Specifically, the presoma is nucleocapsid knot the invention proposes a kind of lithium ion battery anode active material presoma
Structure, the core are carbon source presoma, and the shell is Sn2Co(OH)4CO3And/or Sn2Co(OH)6。
Preferably, the carbon source presoma is one of coal tar pitch, asphalt, phenolic resin, epoxy resin.
Preferably, the average grain diameter of the core is 8 ~ 18 μm.
Preferably, the average grain diameter of the shell is 20 ~ 40nm.
Preferably, the shell with a thickness of 80 ~ 200nm.
Preferably, the weight ratio of the carbon source presoma, tin and cobalt is 97 ~ 85:2 ~ 10:1 ~ 5.
Invention also provides a kind of preparation method of lithium ion battery anode active material presoma, this method packets
It includes:
(1) surface-modified treated carbon source presoma and tin-salt solution, cobalt salt solution are mixed to get mixed liquor,
Mixed liquor is contacted with aqueous slkali, while being heated and being stirred, slurry is obtained；
(2) slurry in step (1) is dried, obtains presoma solid.
It preferably, further include the carbon source presoma after surface modification treatment and tin-salt solution, cobalt in the step (1)
Before salting liquid mixing, the carbon source presoma after surface modification treatment is prepared into milkiness with water solvent, the first dispersant
Liquid A.
Wherein the surface modification treatment of the carbon source presoma in step (1) includes: by carbon source presoma and water solvent, silicon
Alkane coupling agent and the second dispersant and ball milling.Preferably, the carbon source presoma, water solvent, silane coupling agent with
And second dispersing agent weight ratio be 20 ~ 30:80 ~ 100:1 ~ 2:1 ~ 2.
Preferably, the weight ratio of the modified carbon source presoma and the first dispersing agent is 10 ~ 15:1.
Preferably, first dispersing agent, the second dispersing agent be polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol,
One of polyacrylamide, carboxymethyl cellulose are a variety of.
Preferably, the aqueous slkali is one of ammonium bicarbonate soln, ammonia spirit, urea liquid or a variety of；；It is preferred that
, the aqueous slkali is ammonium bicarbonate soln；It is further preferred that in the step (2), side that mixed liquor is contacted with aqueous slkali
Method are as follows: aqueous slkali is added drop-wise in mixed liquor, rate of addition is 5 ~ 10ml/min；The temperature heated in the step (2) is 60 ~
80℃。
Invention further provides a kind of preparation methods of lithium ion battery anode active material, this method comprises:
(1) presoma solid described in claim 1 is dissolved in organic solvent and obtains emulsion B；
(2) graphite is added in emulsion B, carrying out primary heating makes organic solvent volatilize, and then carrying out reheating makes
The melting of carbon source presoma restores under reducing atmosphere after cooling and obtains solid powder；
(3) solid powder progress carbonization treatment is obtained into lithium ion battery anode active material
Wherein, the organic solvent is the naphthalene of carbon tetrachloride or molten condition, and in step (1) presoma solid with have
The weight ratio of solvent is 1:20 ~ 40.
Preferably, in the step (2), the temperature of primary heating is 210~230 DEG C, the time of primary heating be 2h~
3h；The temperature of reheating is 250~280 DEG C, and the time of reheating is 1h~2h.
The present invention provides a kind of lithium ion battery anode active materials, and the lithium ion battery anode active material is by above
Method obtains.
The present invention provides a kind of lithium ion battery negative material, which includes negative electrode active material and bonding
Agent, wherein negative electrode active material is above-described lithium ion battery anode active material.
Invention further provides a kind of negative electrode of lithium ion battery, which includes collector and coating and/or filling
In the negative electrode material on collector, wherein negative electrode material is above-described lithium ion battery negative material.
The present inventor it has been investigated that, by the surface of pitch particle deposit one layer of Sn2Co (OH) 4CO3 and/
Or 6 particle preparation of Sn2Co (OH) obtain be as core, with Sn2Co (OH) 4CO3 and/or Sn2Co (OH) 6 using pitch shell forerunner
Then the presoma is coated on graphite surface by body, carry out under reduction treatment and protective atmosphere by carrying out under reducing atmosphere
Lithium ion battery anode active material is prepared in carbonization treatment, and graphite will not agglomerate in preparation process, and do not need through
The negative electrode active material containing nanoscale tin-cobalt alloy, preparation-obtained lithium-ion electric can also be obtained by crossing subsequent ball-milling treatment
Pond negative electrode active material conducts electricity very well, and volume and capacity ratio is high, and high rate performance is high, and cyclical stability is strong.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is scanning electron microscope (SEM) figure for the presoma solid powder C being prepared in embodiment 1.
Fig. 2 is scanning electron microscope (SEM) figure for the solid powder E being prepared in embodiment 1.
Fig. 3 is the negative electrode of lithium ion battery activity that the solid powder E being prepared in embodiment is obtained after carbonization treatment
Scanning electron microscope (SEM) figure of material.
Fig. 4 is the negative electrode of lithium ion battery activity that the solid powder E being prepared in embodiment is obtained after carbonization treatment
The XRD diagram of material.
Fig. 5 is the cycle performance curve graph for the lithium ion battery that embodiment and comparative example are prepared.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of lithium ion battery anode active material presoma, which is core
Shell structure, the core are carbon source presoma, and the shell is Sn2Co(OH)4CO3And/or Sn2Co(OH)6.Before the negative electrode active material
The core of body is the primary particle of carbon source presoma, and the average grain diameter of the core is 8 ~ 18 μm, the negative electrode active material material precursor
Shell structure be Sn2Co(OH)4CO3Particle and/or Sn2Co(OH)6Particle, the average grain diameter of the shell are 20 ~ 40nm；The thickness of shell
Degree is 80 ~ 200nm.
Wherein the carbon source presoma is one of coal tar pitch, asphalt, phenolic resin, epoxy resin；It is excellent
Choosing uses coal tar pitch.
Preferably, the weight ratio of the carbon source presoma, tin and cobalt is 97 ~ 85:2 ~ 10:1 ~ 5.
The present invention also provides a kind of preparation methods of lithium ion battery anode active material presoma, comprising:
(1) surface-modified treated carbon source presoma and tin-salt solution, cobalt salt solution are mixed to get mixed liquor,
Mixed liquor is contacted with aqueous slkali, while being heated and being stirred, slurry is obtained；
(2) slurry in step (1) is dried, obtains presoma solid.Preferably, the step (1) is gone back
May include, before the carbon source presoma after surface modification treatment is mixed with tin-salt solution, cobalt salt solution, by surface modification treatment
Carbon source presoma and water solvent, the first dispersant afterwards is prepared into emulsion A.Wherein water solvent is that this field is conventional
The water solvent, preferably deionized water；First dispersing agent be polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol,
One of polyacrylamide, carboxymethyl cellulose are a variety of；Preferably, first dispersing agent is polyvinylpyrrolidone；
It is further preferred that the weight ratio of the modified carbon source presoma and the first dispersing agent is 10 ~ 15:1.
Using polyvinylpyrrolidone, dispersion effect in the water solvent of modified coal tar pitch can be made more
It is good.
Wherein, the surface modification treatment of the carbon source precursor in step (1) include: by carbon source presoma and water solvent,
Silane coupling agent and the second dispersant and ball milling.The water solvent is water solvent described in the routine of this field, excellent
It is selected as deionized water.Second dispersing agent is polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyacrylamide, carboxylic first
One of base cellulose is a variety of；Preferably, second dispersing agent is polyvinyl alcohol.Preferably, carbon source presoma, water system
The weight ratio of solvent, silane coupling agent and the second dispersing agent is 20 ~ 30:80 ~ 100:1 ~ 2:1 ~ 2.
It is ball grinding method commonly used in the art that the carbon source presoma, which carries out ball grinding method when surface is modified, is such as added
Entering zirconium ball, and the weight ratio of zirconium ball and ball milling material is 20 ~ 80:1, the revolving speed of ball milling is 160 ~ 300r/min, Ball-milling Time is 3 ~
5h。
Tin-salt solution in above-mentioned steps (1) is the aqueous solution of the soluble pink salt of this field routine, and preferably sulfuric acid is sub-
One of solution of tin, nitric acid stannous solution, stannous chloride solution are a variety of；The further preferably aqueous solution of stannous sulfate；
Cobalt salt solution in above-mentioned steps (1) is the aqueous solution of the soluble cobalt of this field routine, preferably cobaltous sulfate
One of solution, cobalt nitrate solution, cobalt chloride solution are a variety of；The further preferably aqueous solution of cobalt chloride；
Aqueous slkali in above-mentioned steps (1) is one of ammonium bicarbonate soln, ammonia spirit, urea liquid or a variety of；
The preferably aqueous solution of ammonium hydrogen carbonate.
The method that mixed liquor is contacted with aqueous slkali in above-mentioned steps (1) are as follows: aqueous slkali is added drop-wise in mixed liquor, speed is added dropwise
Degree is 5 ~ 10ml/min；The temperature heated in the step (2) is 60 ~ 80 DEG C；Specially aqueous slkali is added drop-wise in mixed liquid B
When metering pump can be used be added dropwise, the speed of dropwise addition is 5 ~ 10ml/min, and dropwise addition while heats simultaneously mixed solution
Stirring；Wherein conventional heating means can be used in heating, it is preferred to use heating water bath, the temperature of heating are 60 ~ 80 DEG C；Stirring speed
Degree is 100r ~ 200/min.
Drying process in above-mentioned steps (2) is the drying means of this field routine, including by the slurry in step (2) into
Row filters, washs and be put into drying box and be dried, and drying temperature is 45 ~ 50 DEG C.
Invention further provides a kind of preparation methods of lithium ion battery anode active material, comprising:
(1) above-mentioned presoma solid is dissolved in the emulsion B that presoma solid and organic solvent are obtained in organic solvent；
Herein, the organic solvent is the naphthalene of carbon tetrachloride or molten condition, and the weight of presoma solid and organic solvent
Amount is than being 1:20 ~ 40, at this point, carbon source presoma is dissolved in organic solvent.
(2) graphite is added in emulsion B, carrying out primary heating makes organic solvent volatilize, and then carrying out reheating makes
The melting of carbon source presoma restores under reducing atmosphere after cooling and obtains solid powder；
(3) solid powder progress carbonization treatment is obtained into lithium ion battery anode active material；
It can be stirred after graphite is added in emulsion B, mixing time is 20min~40min, can make graphite
Fully dispersed, the Sn in emulsion B2Co(OH)4CO3Particle and/or Sn2Co(OH)6Particle is evenly coated at the surface of graphite, shape
It is graphite, outer layer Sn at uniform internal layer2Co(OH)4CO3Particle and/or Sn2Co(OH)6The lotion pearl of particle；Then it carries out
Primary heating, the temperature of primary heating are 210~230 DEG C, and the time of primary heating is 2h~3h；Primary heating makes emulsion
Organic solvent in B evaporates into completely, then carries out reheating, and the temperature of reheating is 250~280 DEG C, reheating
Time is 1h~2h, and reheating makes the softening melting of carbon source presoma.Using such heating means, carbon source forerunner can be made
Body and Sn2Co(OH)4CO3Particle and/or Sn2Co(OH)6Particle forms uniform complex and is coated on the table of graphite well
Face.The step of finally being carried out reduction treatment under reducing atmosphere, is coated on the Sn of graphite surface at this time2Co(OH)4CO3
Grain and/or Sn2Co(OH)6Particle is reduced into tin-cobalt alloy, obtains using graphite as core, with carbon source presoma and tin-cobalt alloy
Uniform complex is the solid powder of clad.Reduction treatment herein include in a hydrogen atmosphere in will using graphite as core, with
Carbon source presoma and Sn2Co(OH)4CO3Particle and/or Sn2Co(OH)6The uniform complex of particle is the solid particle of shell 400
It is restored, is obtained using the uniform complex of carbon source presoma and tin-cobalt alloy as the solid powder of clad at DEG C.By solid
Powder carries out carbonization treatment, and the carbonization treatment is the carbonization treatment means of this field routine, such as before being heated up, in gas
Leading to nitrogen in atmosphere furnace makes oxygen content be maintained at 30ppm hereinafter, then gas vent, holding air inlet are passed through the speed of nitrogen
Rate is 0.3m3/ h, is warming up to 400 DEG C, keeps the temperature 2h, then be warming up to 700 DEG C with the rate of 10 DEG C/min, keeps the temperature 2h, later again with
The rate of temperature rise of 10 DEG C/min is warming up to 900 DEG C, keeps the temperature 1h, naturally cools to room temperature to get lithium-ion electric described herein is arrived
Pond negative electrode active material, the material are core-shell structure, and the core is graphite, and the shell is the uniform of amorphous carbon and tin-cobalt alloy
Complex.
Use method preparation described herein using graphite as core, using the complex of agraphitic carbon and tin-cobalt alloy as shell
Lithium ion battery anode active material, use first prepare using carbon source presoma as core, with Sn2Co (OH) 4CO3 particle and/or
6 particle of Sn2Co (OH) is the presoma of shell, is then mixed in organic solvent with graphite, so that pitch and Sn2Co (OH) 4CO3
Particle and/or 6 particle of Sn2Co (OH) form uniform cladding in graphite surface, and graphite is evenly dispersed in preparation process, is not in
Caking phenomenon is not needed through subsequent ball-milling treatment, and technique is more simple, and tin-cobalt alloy particle is coated on stone with nanoscale
Black surface, so that the negative electrode active material particle being prepared is uniform, the negative electrode material being prepared conducts electricity very well, volume ratio
Capacity is high, and high rate performance is high, and cyclical stability is strong.
The present invention also provides a kind of lithium ion battery anode active materials, are prepared by above method.The cathode
Active material is core-shell structure, and the core is graphite, and the shell is the uniform complex of amorphous carbon and tin-cobalt alloy.
Invention further provides a kind of lithium ion battery negative material, the negative electrode material include negative electrode active material and
Bonding agent, the negative electrode active material are lithium ion battery anode active material provided by the present application, and the binder is ability
The binder of domain routine can be carboxymethylcellulose sodium, Kynoar, polytetrafluoroethylene (PTFE), sodium alginate, Sodium Polyacrylate
One of or it is a variety of.In the negative electrode material, the weight ratio of the negative electrode active material and binder is 85 ~ 90:15 ~ 10.
The present invention also provides a kind of negative electrode of lithium ion battery, which includes collector and coating and/or is filled in collection
Negative electrode material on fluid, which is characterized in that the negative electrode material that described negative electrode material the application proposes, negative electrode of lithium ion battery
Preparation method is not limited thereto, and is the preparation method of this field routine, this will not be detailed here.
The present invention will be described in detail by way of examples below.
Embodiment 1
(1) 50g coal tar pitch, 300g deionized water is taken to be put into ball grinder, then add 5% it is silane coupled
Agent, 5% polyvinyl alcohol, be put into zirconium ball, ratio of grinding media to material 5:1.Revolving speed 120r/min, 4 ~ 8h of ball milling, then be added water solvent,
Polyvinylpyrrolidone is stirred to obtain mixed liquor A；Cobalt chloride hexahydrate 13.39g is weighed, stannous sulfate 18.13g is dissolved in
After being configured to aqueous solution in deionized water, sequentially adds and obtain mixed liquid B in mixed liquor A, it is using metering pump that ammonium hydrogen carbonate is molten
Liquid is slowly added dropwise in mixed liquid B and stirs to get slurry.Wherein rate of addition is 8ml/min, and whole process is added using water-bath
Heat, heating temperature are 75 DEG C, mixing speed 180r/min；Resulting precipitate slurry is filtered using circulating water type vacuum pump
Processing, is washed three times repeatedly, suction filtration gained cake solids is put into 45 DEG C of vacuum oven is dried later, obtained
To presoma solid powder；
(2) it weighs 80g naphthalene and is put into cladding tank (cladding tank is heated using circulating hot oil), be warming up to 90 DEG C, keep naphthalene complete
Melt, presoma solid powder C8g is taken to be added in the naphthalene melted, stirring forms it into emulsion.It is spherical natural to weigh 100g
Graphite is added in above-mentioned emulsion, and being stirred continuously makes it be uniformly dispersed, 20 ~ 40min of the process duration, keeps temperature 90
℃.It is warming up to 210 DEG C later, keeps the temperature 2h, is evaporated organic solvent naphthalene, increases the temperature to 250 DEG C later, keeps the temperature 1h.Natural cooling
To room temperature, obtained solid powder is carried out at 400 DEG C to reduction treatment in hydrogen atmosphere and obtains solid powder；
(3) solid powder E is subjected to the carbonization treatment means that carbonization treatment is this field routine, such as is carrying out heating up it
Before, nitrogen is led in atmosphere furnace makes oxygen content be maintained at 30ppm hereinafter, then gas vent, holding air inlet are passed through
The rate of nitrogen is 0.3m3/ h is warming up to 400 DEG C, keeps the temperature 2h, then be warming up to 700 DEG C with the rate of 10 DEG C/min, keeps the temperature 2h,
900 DEG C are warming up to the rate of temperature rise of 10 DEG C/min again later, 1h is kept the temperature, naturally cools to room temperature, obtain negative electrode of lithium ion battery
Active material C1.
(4) negative electrode active material A1, sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR), deionized water are pressed 4:
The tabletting after mixing of the weight ratio of 2.4:0.1:2.4,120 DEG C of vacuum drying obtain work pole piece for 24 hours；It is with metal lithium sheet
To electrode, celgard2400 polypropylene porous film is diaphragm, the ethylene carbonate (EC) and dimethyl of 1mol/L LiPF6
The mixed solution (volume ratio is=1: 1) of carbonic ester (DMC) is that electrolyte assembles in the glove box full of argon gas, obtains electricity
Pond sample S1.
Embodiment 2
It is same as Example 1, unlike, stannous sulfate is substituted with nitric acid tin in step (1), substitutes six water with cobalt nitrate
Cobalt chloride is closed, battery S2 is obtained.
Embodiment 3
It is same as Example 1, unlike, the stannous sulfate being added in step (1) is 15.4g, six hydration chlorine of addition
Change cobalt is 21.1g, obtains battery S3.
Embodiment 4
It is same as Example 1, unlike, polyvinylpyrrolidone is replaced using polyvinyl alcohol, obtains battery S4.
Embodiment 5
It is same as Example 1, unlike, silane coupling agent is substituted using dodecyl sodium sulfate, obtains battery S5.
Embodiment 6
It is same as Example 1, unlike, ammonium hydrogen carbonate is replaced using ammonia spirit, obtains battery S6.
Embodiment 7
It is same as Example 1, unlike, ammonium hydrogen carbonate is replaced using urea liquid, obtains battery S7.
Embodiment 8
It is same as Example 1, unlike, replace the naphthalene of melting as organic solvent using carbon tetrachloride, obtains battery
S8。
Embodiment 9
It is same as Example 1, unlike, 12 g of coal tar pitch is taken, stannous sulfate 16.1g is taken, takes six chloride hydrates
Cobalt 21.8g takes graphite 100g, obtains battery S9.
Comparative example 1
Negative electrode active material is prepared using the method in CN200610020272.3, and is used for preparation lithium-ion negative pole
And it is further prepared into battery, obtain battery DS1.
Performance test
1, sem test
Using scanning electron microscope respectively to presoma solid, solid powder and the negative electrode active material A1 in embodiment 1 into
Row test, obtains Fig. 1-Fig. 3.
2, cycle performance is tested
Charge-discharge test, discharge cut-off voltage are carried out under the conditions of 0.2C charge-discharge magnification to the battery S1 in embodiment 1
5mV, charge cutoff voltage 2V carry out cycle performance test, obtain Fig. 4.
3, charge-discharge performance is tested
Battery S1-S9, D1 are subjected to electrochemical property test in blue odd test cabinet with room temperature environment, charging and discharging currents are
0.1 ~ 0.3C, blanking voltage are 0.005 ~ 2V, and test result is shown in Table 1:
Table 1
As it can be seen from table 1 as it can be seen from table 1 negative electrode active material is first prepared using method of the present invention
Material precursor, then using the presoma be raw material be prepared using graphite as core, with the compound of amorphous carbon and tin-cobalt alloy
Body be shell negative electrode active material, which is prepared into cathode and is used for battery, obtained battery: first charge discharge efficiency
Up to 93%, much higher than the 40-70% of existing tin negative pole material.Capacity retention ratio is also maintained at 85% or more after 50 circulations,
The done battery of the material described above has lower irreversible capacity, and with more stable while having taken into account high capacity
Cycle performance.
From Fig. 1-Fig. 3 it can be seen that solid powder C be nanoscale tin cobalt precipitating uniformly disperse and adhere to pitch or
The surface of resin, during subsequent cladding, tin cobalt precipitates particle and uniformly adheres to spherical natural graphite by pitch or resin
Surface, after high temperature reduction carbonization treatment, the tin-cobalt alloy in carbon coating shell is still nanoscale.
From Fig. 4-Fig. 5 it can be seen that the done negative electrode material of the present invention, 90% or more first charge discharge efficiency with higher are lower
Irreversible capacity, side reaction is more caused by improving while having taken into account high capacity because of volume expansion, capacitance loss is very fast
The problem of, reach higher cyclical stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (20)
1. a kind of lithium ion battery anode active material presoma, which is characterized in that the negative electrode active material material precursor is nucleocapsid
Structure, the core are carbon source presoma, and the shell is Sn2Co(OH)4CO3And/or Sn2Co(OH)6。
2. lithium ion battery anode active material presoma according to claim 1, which is characterized in that the carbon source forerunner
Body is one of coal tar pitch, asphalt, phenolic resin, epoxy resin.
3. lithium ion battery anode active material presoma according to claim 1, which is characterized in that the core is averaged
Partial size is 8 ~ 18 μm.
4. lithium ion battery anode active material presoma according to claim 1, which is characterized in that the shell is averaged
Partial size is 20 ~ 40nm.
5. lithium ion battery anode active material presoma according to claim 1, which is characterized in that the thickness of the shell
For 80 ~ 200nm.
6. lithium ion battery anode active material presoma according to claim 1, which is characterized in that the carbon source forerunner
The weight ratio of body, tin and cobalt is 97 ~ 85:2 ~ 10:1 ~ 5.
7. a kind of preparation method of lithium ion battery anode active material presoma, characterized by comprising:
(1) it by carbon source presoma and water solvent, silane coupling agent and the second dispersant and ball milling, obtains to surface and changes
Property treated carbon source presoma；
(2) surface-modified treated carbon source presoma and tin-salt solution, cobalt salt solution are mixed to get mixed liquor, will mixed
It closes liquid to contact with aqueous slkali, while being heated and being stirred, obtain slurry；
(3) slurry in step (2) is dried, obtains presoma solid.
8. the preparation method of lithium ion battery anode active material presoma according to claim 7, which is characterized in that institute
Stating step (2) further includes, before the carbon source presoma after surface modification treatment is mixed with tin-salt solution, cobalt salt solution, by surface
Carbon source presoma and water solvent, the first dispersant after modification are prepared into emulsion A.
9. the preparation method of lithium ion battery anode active material presoma according to claim 8, which is characterized in that institute
The weight ratio for stating carbon source presoma, water solvent, silane coupling agent and the second dispersing agent is 20 ~ 30:80 ~ 100:1 ~ 2:1 ~ 2.
10. the preparation method of lithium ion battery anode active material presoma according to claim 8, which is characterized in that
The weight ratio of the modified carbon source presoma and the first dispersing agent is 10 ~ 15:1.
11. the preparation method of lithium ion battery anode active material presoma according to claim 9, which is characterized in that
First dispersing agent, the second dispersing agent are polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyacrylamide, carboxylic first
One of base cellulose is a variety of.
12. the preparation method of lithium ion battery anode active material presoma according to claim 7, which is characterized in that
The aqueous slkali is one of ammonium bicarbonate soln, ammonia spirit, urea liquid or a variety of.
13. the preparation method of lithium ion battery anode active material presoma according to claim 7, which is characterized in that
In the step (2), method that mixed liquor is contacted with aqueous slkali are as follows: aqueous slkali is added drop-wise in mixed liquor, rate of addition is 5 ~
10ml/min；The temperature heated in the step (3) is 60 ~ 80 DEG C.
14. a kind of preparation method of lithium ion battery anode active material, which is characterized in that this method comprises:
(1) presoma solid described in claim 1 is dissolved in organic solvent and obtains emulsion B；
(2) graphite is added in emulsion B, carrying out primary heating makes organic solvent volatilize, and then carrying out reheating makes carbon source
Presoma melting restores under reducing atmosphere after cooling and obtains solid powder；
(3) solid powder progress carbonization treatment is obtained into lithium ion battery anode active material.
15. the preparation method of lithium ion battery anode active material according to claim 14, which is characterized in that described to have
Solvent is the naphthalene of carbon tetrachloride or molten condition.
16. the preparation method of lithium ion battery anode active material according to claim 14, which is characterized in that the step
Suddenly the weight ratio of presoma solid and organic solvent is 1:20 ~ 40 in (1).
17. the preparation method of lithium ion battery anode active material according to claim 14, which is characterized in that the step
Suddenly in (2), the temperature of primary heating is 210~230 DEG C, and the time of primary heating is 2h~3h；The temperature of reheating is 250
~280 DEG C, the time of reheating is 1h~2h.
18. the lithium ion battery anode active material that the method as described in any one of claim 14-17 is prepared.
19. a kind of lithium ion battery negative material, which includes negative electrode active material and bonding agent, which is characterized in that
The negative electrode active material is lithium ion battery anode active material described in claim 18.
20. a kind of negative electrode of lithium ion battery, which includes collector and coating and/or the cathode material being filled on collector
Material, which is characterized in that the negative electrode material is lithium ion battery negative material described in claim 19.
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| CN107026261B (en) * | 2017-01-12 | 2020-02-07 | 天津大学 | Preparation and application of tin-cobalt alloy embedded carbon nano composite material |
| KR102171095B1 (en) | 2017-06-09 | 2020-10-28 | 주식회사 엘지화학 | Negative electrode active material, negative electrode and lithium secondary battery comprising the same |
| CN109942031A (en) * | 2019-03-20 | 2019-06-28 | 江西理工大学 | A kind of nickel-base anode material precursor and preparation method thereof |
| CN111434609B (en) * | 2019-12-27 | 2022-09-20 | 蜂巢能源科技有限公司 | Pre-lithiated negative electrode active material, preparation method thereof, negative plate and lithium ion battery |
| CN114094110B (en) * | 2022-01-24 | 2022-04-22 | 河南电池研究院有限公司 | Graphite cathode for solid lithium ion battery |
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