CN106531980A - Negative electrode material for lithium-ion battery and preparation method and application of negative electrode material - Google Patents
Negative electrode material for lithium-ion battery and preparation method and application of negative electrode material Download PDFInfo
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Abstract
The invention discloses a negative electrode material for a lithium-ion battery and a preparation method and application of the negative electrode material. The method comprises the steps of carrying out wet ball-milling on silicon powder and a dispersing agent during preparation to obtain silicon slurry; mixing the silicon slurry with graphite and a conductive agent evenly and carrying out spray drying to obtain near-spherical particles; carrying out mechanical integration on the near-spherical particles to obtain a precursor A; mixing the precursor A with resin VC, carrying out mechanical integration and carrying out coating in a coating kettle to obtain a precursor B; mixing the precursor B with asphalt VC, carrying out mechanical integration and carrying out coating in the coating kettle to obtain a precursor C; and sintering, carbonizing and screening the precursor C in an inert atmosphere to obtain the negative electrode material for the lithium-ion battery. The negative electrode material for the lithium-ion battery prepared by the preparation method is used for preparing the lithium-ion battery. The negative electrode material for the lithium-ion battery has the characteristics of small specific surface area, high initial efficiency, good circulation, high rate capability and the like, and the preparation method disclosed by the invention is suitable for industrial production.
Description
Technical field
The present invention relates to field of lithium ion battery, specifically a kind of lithium ion battery negative material and preparation method thereof and should
With.
Background technology
The theoretical capacity of graphite is only 372mAh/g, and the theoretical capacity of silicon reaches 4200mAh/g, is to improve lithium ion battery
Energy density, studied more and more to siliceous negative material in recent years both at home and abroad, and its research is had focused largely on again to silicon discharge and recharge
During in the volumetric expansion that produces.
On silicon charge and discharge process expansion issues are solved, one of more research is silicon nanorize, silicon is combined with matrix delays
The means such as punching expansion；Have in research and reach the adhesion strengthened between silicon and matrix, such as application number using means such as mechanical fusions
201310703654.6 patent of invention, carries out mechanical fusion and pitch-coating using the hollow plumbago to being dispersed with nano silica fume
Mode prepare lithium ion battery negative material.Although the invention can reduce to a certain extent silicon expansion, improve nano-silicon with
The adhesion of graphite matrix, but there is nano silica fume in matrix surface poor dispersion, it cannot be guaranteed that Colophonium is firmly coated on
The shortcomings of material surface, and using ball milling method come to prepare hollow plumbago be a kind of ideal style, it is actual to be difficult operation.
The content of the invention
The technical problem to be solved is to overcome existing nano-silicon to disperse uneven, adhesion not with matrix
By force, carbon coating effect is poor, the problems such as be unable to industrialization, there is provided a kind of specific surface area is little, first efficiency high, circulate, it is forthright again
Lithium ion battery negative material that can be high and its preparation method and application, to solve the problems, such as to propose in above-mentioned background technology.
For achieving the above object, the present invention provides following technical scheme：
A kind of preparation method of lithium ion battery negative material, comprises the following steps：
(1) silica flour and dispersant are carried out into wet ball grinding, obtains silicon slurry；
(2) after mixed homogeneously silicon slurry with graphite, conductive agent, it is spray-dried, is obtained near-spherical granule；
(3) near-spherical granule is carried out into mechanical fusion and obtains precursor A；
(4) mechanical fusion will be carried out after precursor A and resin VC batch mixings, then coated in cladding kettle, obtain presoma
B；
(5) mechanical fusion will be carried out after precursor B and Colophonium VC batch mixings, then coated in cladding kettle, obtain presoma
C；
(6) presoma C is sintered under an inert atmosphere, carbonization, screening obtain final product lithium ion battery negative material.
As further scheme of the invention：In step (1), the wet ball grinding is that silica flour is milled to D50 particle diameters to be
50-350nm；Preferably 150-250nm, the particle diameter of silicon are less, volumetric expansion occurs and changes less, be more conducive to battery to follow
Ring, but the Ball-milling Time needed for which is long, and energy consumption is too high, is unfavorable for industrialized production；The particle diameter of silicon is excessive, and its volumetric expansion becomes
Change is larger, and battery capacity can be caused to decay rapidly, therefore selects the D50 particle diameters for being milled to silica flour have work concurrently for 50-350nm
Skill industrialization and the purpose of reduction cell expansion degree, realize superior technique effect.The use of dispersant can be in silica flour ball
Reduce or suppress reuniting again for nano-silicon during mill, the dispersant is sodium carboxymethyl cellulose (abbreviation CMC), polyvinyl alcohol
In in water soluble dispersing agents such as (abbreviation PVA) one or several, the addition of dispersant is the 0.01- of silicon slurry gross mass
0.25%；The content of dispersant can not be too high, the easy plug nozzle of slurry otherwise in subsequent spray dry run；In silicon slurry
The mass concentration of silicon be 5-15%, the too high easy blocking ball-grinding machine of silicon slurry concentration, concentration too it is low causes efficiency low cost rise
It is high.
As further scheme of the invention：In step (2), the consumption of silicon slurry is silicon slurry, graphite, conductive agent three
The 12-23% of gross mass, the consumption of the graphite is silicon slurry, graphite, the 75-85% of conductive agent three's gross mass, described to lead
Electric agent consumption is silicon slurry, graphite, the 0.5-3.5% of conductive agent three's gross mass；(consumption of silicon slurry is with silica flour contained therein
Quality calculated for standard, the consumption of the silica flour is silica flour, graphite, the 12-23% of conductive agent three's gross mass, described
The consumption of graphite be silica flour, graphite, the 75-85% of conductive agent three's gross mass, the conductive agent consumption be silica flour, graphite, lead
The 0.5-3.5% of electric agent three gross mass；)；The graphite is Delanium and/or native graphite, and particle diameter is 2～10 μm；Institute
It is conductive agent commonly used in the art to state conductive agent, such as carbon black Super-P etc..
As further scheme of the invention：In step (3), near-spherical granule is in mechanical fusion equipment centrifugal action
Under, granule more uniform between rotor and stator can be squeezed under being driven at a high speed, frictional force, therefore enhance granule table
Face and the adhesion of internal nano-silicon and graphite surface, the time of fusion is 5-60min；Preferably 20-40min, fusion
Time can not be oversize, and otherwise extruding, frictional force are easily destroyed granule-morphology, and the time too short effect for not having fusion, after fusion
The particle diameter of gained precursor A is 6-13 μm.
As further scheme of the invention：In step (4), the resin is phenolic resin, epoxy resin, polytetrafluoroethyl-ne
In alkene one or more, the mass ratio of resin and precursor A is 1:3-1:10；Preferably 1:5-1:10, VC mixing times
It is defined by material mix homogeneously, the time of fusion is 5-30min；The cladding is heat treated under an inert atmosphere, plus
Hot temperature is 300-700 DEG C, is incubated 1-5 hours；The particle diameter of the precursor B is 8-15 μm.
As further scheme of the invention：In step (5), the Colophonium is any one in selected from coal tar pitch and petroleum asphalt
Kind, the asphalt softening point is 120-300 DEG C, and Colophonium is 1 with the mass ratio of precursor B:2-1:6；Preferably 1:3-1:4,
VC mixing times are defined by material mix homogeneously, and the time of fusion is 10-50min；The cladding is to add under an inert atmosphere
Hot temperature is 400-600 DEG C, is incubated 2-6 hours；The particle diameter of the precursor C is 10-17 μm.
As further scheme of the invention：In step (6), sintering, the temperature of carbonization are 900～1100 DEG C, sintering, charcoal
The time of change is 6～10 hours, and after screening, gained lithium ion battery negative material particle diameter is 11-18 μm.
The second object of the present invention is, there is provided according to above-mentioned lithium ion battery negative material preparation method obtained in lithium
Ion battery cathode material.
The third object of the present invention is, there is provided above-mentioned lithium ion battery negative material in lithium ion battery is prepared should
With.
The fourth object of the present invention is, there is provided a kind of lithium ion battery, described lithium ion battery include above-mentioned lithium from
Sub- cell negative electrode material.
The present invention innovation be：1st, graphite can buffer the expansion of nano silica fume as matrix, by spray dried
It is dry to make nano-silicon, conductive agent be evenly distributed on graphite surface；2nd, the material after spray drying is carried out mechanical fusion make nano-silicon with
Graphite matrix adhesion is higher；3rd, the hard carbon material of resin-coated formation the surface of nano-silicon and graphite play with electrolyte every
From effect, stable SEI films are advantageously formed, improve the coulombic efficiency first of material；4th, coat Colophonium outside hard carbon material again
Soft carbon material is formed, can play reduces the specific surface area effect of hard carbon, while soft charcoal material electrolyte resistance is also relatively good；5th, to receiving
Successively cladding hard carbon and soft charcoal play double shielding effect to material surface for rice silicon and graphite surface, and coat in above-mentioned 2 step
During using mechanical fusion be conducive to improve covered effect.
Compared with prior art, the invention has the beneficial effects as follows：
1. the lithium ion battery negative material of the present invention have that specific surface area is little, nano-silicon is dispersed in matrix surface,
Material surface energy formed stable SEI films, first efficiency high, circulate, the features such as high rate performance is high.
2. the preparation method of the present invention is adapted to industrialized production.
Description of the drawings
Fig. 1 is lithium ion battery negative material scanning electron microscope (SEM) figure obtained in embodiment 1.
First charge-discharge curve charts of the Fig. 2 for lithium ion battery obtained in embodiment 2.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based in the present invention
Embodiment, the every other embodiment obtained under the premise of creative work is not made by those of ordinary skill in the art, all
Belong to the scope of protection of the invention.
Raw material purchase producer and its model used in following examples of the present invention is as follows：
Silica flour：Purchased from hair powder body Materials Co., Ltd of upper marine oil enterprise；
Delanium and native graphite：Self-produced purchased from Shanghai Shanshan Science and Technology Co., Ltd, model 3H series is serial with RG.
Asphalt and coal tar pitch：Purchased from Sinosteel Corporation's mid temperature pitch, hard pitch.
Embodiment 1
(1) 5kg silica flours are taken with water as medium, and it is 150nm wet ball grinding to be carried out to D50 particle diameters, obtains siliceous 10%, dispersant
0.1% silicon slurry；
(2) by above-mentioned silicon slurry, the Delanium that 22.222kg particle diameter D50 are 5 μm and 556g conductive blacks in high speed point
It is sufficiently mixed in scattered machine uniformly, mixed slurry is spray-dried, the inlet temperature for controlling spray dryer is 270 DEG C, is gone out
Mouth temperature is 105 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical granule；
(3) near-spherical granule is carried out into mechanical fusion, the warm time is 30min, and warm speed is 2000 revs/min, obtains grain
Footpath is 9 μm of precursor A；
(4) by precursor A and phenolic resin according to 1：5 mass ratio mechanical fusion again after VC batch mixer mix homogeneously,
Time of fusion is 30min, and fusion material is heated to 400 DEG C in a nitrogen atmosphere in cladding kettle while stirring, is incubated 3 hours, obtains
Particle diameter is 10 μm of precursor B；
(5) by asphalt that precursor B and softening point are 150 DEG C according to 1：4 mass ratio is equal with the mixing of VC batch mixers
Mechanical fusion again after even, time of fusion is 45min, and fusion material is heated to 450 in a nitrogen atmosphere in cladding kettle while stirring
DEG C, 3 hours are incubated, the presoma C that particle diameter is 12 μm is obtained；
(6) presoma C 1000 DEG C of sintering, carbonization, screenings in the box Si-Mo rod or resistance wire furnace of nitrogen atmosphere are obtained final product
To the finished product that particle diameter is 15 μm.
The SEM of obtained lithium ion battery negative material is schemed as shown in figure 1, first charge-discharge curve is as shown in Fig. 2.
Embodiment 2
91 parts of the lithium ion battery negative material of above-described embodiment 1, is added thereto to containing 9 parts of CMC/Super-P/SBR (matter
Amount compares 4.5:2.0:2.5) 200 parts of aqueous solution, forms slurry after mixing；
The slurry is coated on the Copper Foil that thickness is 15 μm, drying, roll-forming are electrode slice.It is right with lithium paper tinsel
Electrode, constitutes lithium rechargeable battery with copper foil electrode obtained above.Electrolyte used be vinyl carbonate containing solvent (EC)/
Dimethyl carbonate (DMC)/(volume ratio is 1 to Ethyl methyl carbonate (EMC):1:1), the lithium hexafluoro phosphates of 1mol/L containing electrolyte
(LiPF6) solution being configured to.Using three layers of micro-pore septum of polypropylene, polyethylene/polypropylene (PP/PE/PP), thickness is 20 μ
m.Test charging and discharging currents density is 0.6mA/cm2, cut-off charging/discharging voltage is 0.005-2.000V.
Determine the initial capacity of the lithium ion battery, coulombic efficiency, the capability retention after circulation in 200 weeks and 5C multiplying powers
As shown in table 1.
Embodiment 3
(1) 5kg silica flours are taken with water as medium, and it is 50nm wet ball grinding to be carried out to D50 particle diameters, obtains siliceous 5%, dispersant
0.01% silicon slurry；
(2) by above-mentioned silicon slurry, the Delanium that 35.417kg particle diameter D50 are 2 μm and 1250g conductive blacks in high speed point
It is sufficiently mixed in scattered machine uniformly, mixed slurry is spray-dried, the inlet temperature for controlling spray dryer is 270 DEG C, is gone out
Mouth temperature is 105 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical granule；
(3) near-spherical granule is carried out into mechanical fusion, the warm time is 5min, and warm speed is 2000 revs/min, obtains particle diameter
For 6 μm of precursor A；
(4) by precursor A and epoxy resin according to 1：10 mass ratio mechanical fusion again after VC batch mixer mix homogeneously,
Time of fusion is 5min, and fusion material is heated to 300 DEG C in a nitrogen atmosphere in cladding kettle while stirring, is incubated 1 hour, obtains grain
Footpath is 8 μm of precursor B；
(5) by coal tar pitch that precursor B and softening point are 120 DEG C according to 1：6 mass ratio VC batch mixer mix homogeneously
Mechanical fusion again, time of fusion is 10min, and fusion material is heated to 400 DEG C in a nitrogen atmosphere in cladding kettle while stirring, protects
Temperature 2 hours, obtains the presoma C that particle diameter is 10 μm；
(6) presoma C 900 DEG C of sintering, carbonization, screenings in the box Si-Mo rod or resistance wire furnace of nitrogen atmosphere are obtained
Particle diameter is 11 μm of finished product.
According to 2 identical method assembled battery of embodiment and tested, its result is as shown in table 1.
Embodiment 4
(1) 5kg silica flours are taken with water as medium, and it is 350nm wet ball grinding to be carried out to D50 particle diameters, obtains siliceous 15%, dispersant
0.25% silicon slurry；
(2) by above-mentioned silicon slurry, the native graphite that 16.3043kg particle diameter D50 are 10 μm and 435g conductive blacks at a high speed
It is sufficiently mixed in dispersion machine uniformly, mixed slurry is spray-dried, the inlet temperature for controlling spray dryer is 270 DEG C,
Outlet temperature is 105 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical granule；
(3) near-spherical granule is carried out into mechanical fusion, the warm time is 60min, and warm speed is 2000 revs/min, obtains grain
Footpath is 13 μm of precursor A；
(4) by precursor A and politef according to 1：With after VC batch mixer mix homogeneously, machinery melts 3 mass ratio again
Close, time of fusion is 30min, fusion material is heated to 700 DEG C in a nitrogen atmosphere in cladding kettle while stirring, is incubated 5 hours,
Obtain the precursor B that particle diameter is 15 μm；
(5) by coal tar pitch that precursor B and softening point are 300 DEG C according to 1：2 mass ratio VC batch mixer mix homogeneously
Mechanical fusion again, time of fusion is 50min, and fusion material is heated to 600 DEG C in a nitrogen atmosphere in cladding kettle while stirring, protects
Temperature 6 hours, obtains the presoma C that particle diameter is 17 μm；
(6) presoma C 1100 DEG C of sintering, carbonization, screenings in the box Si-Mo rod or resistance wire furnace of nitrogen atmosphere are obtained final product
To the finished product that particle diameter is 18 μm.
According to 2 identical method assembled battery of embodiment and tested, its result is as shown in table 1.
Embodiment 5
(1) 5kg silica flours are taken with water as medium, and it is 100nm wet ball grinding to be carried out to D50 particle diameters, obtains siliceous 8%, dispersant
0.05% silicon slurry；
(2) by above-mentioned silicon slurry, the Delanium that 18.571kg particle diameter D50 are 4 μm and 238g conductive blacks in high speed point
It is sufficiently mixed in scattered machine uniformly, mixed slurry is spray-dried, the inlet temperature for controlling spray dryer is 270 DEG C, is gone out
Mouth temperature is 105 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical granule；
(3) near-spherical granule is carried out into mechanical fusion, the warm time is 20min, and warm speed is 2000 revs/min, obtains grain
Footpath is 8 μm of precursor A；
(4) by precursor A and phenolic resin according to 1：4 mass ratio mechanical fusion again after VC batch mixer mix homogeneously,
Time of fusion is 10min, and fusion material is heated to 500 DEG C in a nitrogen atmosphere in cladding kettle while stirring, is incubated 2 hours, obtains
Particle diameter is 9 μm of precursor B；
(5) by asphalt that precursor B and softening point are 200 DEG C according to 1：3 mass ratio is equal with the mixing of VC batch mixers
Even mechanical fusion again, time of fusion is 20min, and fusion material is heated to 500 DEG C in a nitrogen atmosphere in cladding kettle while stirring,
Insulation 4 hours, obtains the presoma C that particle diameter is 13 μm；
(6) presoma C 950 DEG C of sintering, carbonization, screenings in the box Si-Mo rod or resistance wire furnace of nitrogen atmosphere are obtained
Particle diameter is 12 μm of finished product.
According to 2 identical method assembled battery of embodiment and tested, its result is as shown in table 1.
Embodiment 6
(1) 5kg silica flours are taken with water as medium, and it is 250nm wet ball grinding to be carried out to D50 particle diameters, obtains siliceous 13%, dispersant
0.2% silicon slurry；
(2) by above-mentioned silicon slurry, 30.741kg particle diameter D50 are that 8 μm of artificial native graphite and 1.296g conductive blacks exist
It is sufficiently mixed in high speed dispersor uniformly, mixed slurry is spray-dried, the inlet temperature for controlling spray dryer is 270
DEG C, outlet temperature is 105 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical granule；
(3) near-spherical granule is carried out into mechanical fusion, the warm time is 240min, and warm speed is 2000 revs/min, obtains grain
Footpath is 10 μm of precursor A；
(4) by precursor A and phenolic resin according to 1：7 mass ratio mechanical fusion again after VC batch mixer mix homogeneously,
Time of fusion is 20min, and fusion material is heated to 600 DEG C in a nitrogen atmosphere in cladding kettle while stirring, is incubated 4 hours, obtains
Particle diameter is 12 μm of precursor B；
(5) by asphalt that precursor B and softening point are 250 DEG C according to 1：5 mass ratio is equal with the mixing of VC batch mixers
Even mechanical fusion again, time of fusion is 30min, and fusion material is heated to 550 DEG C in a nitrogen atmosphere in cladding kettle while stirring,
Insulation 5 hours, obtains the presoma C that particle diameter is 15 μm；
(6) presoma C 1050 DEG C of sintering, carbonization, screenings in the box Si-Mo rod or resistance wire furnace of nitrogen atmosphere are obtained final product
To the finished product that particle diameter is 14 μm.
According to 2 identical method assembled battery of embodiment and tested, its result is as shown in table 1.
Embodiment 7
(1) 5kg silica flours are taken with water as medium, and it is 200nm wet ball grinding to be carried out to D50 particle diameters, obtains siliceous 14%, dispersant
0.05% silicon slurry；
(2) by above-mentioned silicon slurry, the Delanium that 28.1667kg particle diameter D50 are 6 μm and 167g conductive blacks in high speed point
It is sufficiently mixed in scattered machine uniformly, mixed slurry is spray-dried, the inlet temperature for controlling spray dryer is 270 DEG C, is gone out
Mouth temperature is 105 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical granule；
(3) near-spherical granule is carried out into mechanical fusion, the warm time is 50min, and warm speed is 2000 revs/min, obtains grain
Footpath is 12 μm of precursor A；
(4) by precursor A and phenolic resin according to 1：9 mass ratio mechanical fusion again after VC batch mixer mix homogeneously,
Time of fusion is 25min, and fusion material is heated to 400 DEG C in a nitrogen atmosphere in cladding kettle while stirring, is incubated 3 hours, obtains
Particle diameter is 14 μm of precursor B；
(5) by asphalt that precursor B and softening point are 280 DEG C according to 1：4.5 mass ratio is mixed with VC batch mixers
Uniform mechanical fusion again, time of fusion is 40min, and fusion material is heated to 480 in a nitrogen atmosphere in cladding kettle while stirring
DEG C, 43 hours are incubated, the presoma C that particle diameter is 16 μm is obtained；
(6) presoma C 1000 DEG C of sintering, carbonization, screenings in the box Si-Mo rod or resistance wire furnace of nitrogen atmosphere are obtained final product
To the finished product that particle diameter is 16 μm.
According to 2 identical method assembled battery of embodiment and tested, its result is as shown in table 1.
Comparative example 1
Comparative example 1 is for adopting spray drying compared with Example 1, but by the nano-silicon of equal proportion amount, stone
Ink and the direct mechanical fusion of conductive agent, it is subsequently not resin-coated, only coat Colophonium once, finally sintering, the lithium that obtains of screening from
Sub- cell negative electrode material.
(1) it is 150nm silica flours to take 5kg and be milled to D50 particle diameters, and 22.222kg particle diameter D50 are 5 μm of Delanium and 556g
Conductive black mix homogeneously in VC batch mixers.
(2) by compound mechanical fusion in (1), the warm time is 30min, and warm speed is 2000 revs/min, and obtaining particle diameter is
4 μm of precursor A；
(3) by asphalt that precursor A and softening point are 150 DEG C according to 1：4 mass ratio is equal with the mixing of VC batch mixers
Mechanical fusion again after even, time of fusion is 45min, and fusion material is heated to 450 in a nitrogen atmosphere in cladding kettle while stirring
DEG C, 3 hours are incubated, the precursor B that particle diameter is 8 μm is obtained；
(4) precursor B 1000 DEG C of sintering, carbonization, screenings in the box Si-Mo rod or resistance wire furnace of nitrogen atmosphere are obtained final product
To the finished product that particle diameter is 9 μm.
According to 2 identical method assembled battery of embodiment and tested, its result is as shown in table 2.
Comparative example 2
Compared with Example 1, comparative example 2 is only to remove the mechanical fusion in 3 steps, using common machinery
Mixed method, unclassified stores ratio and scheme do not change and prepare cell negative electrode material.
(1) 5kg silica flours are taken with water as medium, and it is 150nm wet ball grinding to be carried out to D50 particle diameters, obtains siliceous 10%, dispersant
0.1% silicon slurry；
(2) by above-mentioned silicon slurry, the Delanium that 22.222kg particle diameter D50 are 5 μm and 556g conductive blacks in high speed point
It is sufficiently mixed in scattered machine uniformly, mixed slurry is spray-dried, the inlet temperature for controlling spray dryer is 270 DEG C, is gone out
Mouth temperature is 105 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical granule；
(4) by near-spherical granule and phenolic resin according to 1：5 mass ratio with after VC batch mixer mix homogeneously in nitrogen gas
400 DEG C are heated to while stirring in cladding kettle under atmosphere, are incubated 3 hours, are obtained the precursor B that particle diameter is 11 μm；
(5) by asphalt that precursor B and softening point are 150 DEG C according to 1：4 mass ratio is equal with the mixing of VC batch mixers
450 DEG C are heated to while stirring in cladding kettle in a nitrogen atmosphere after even, are incubated 3 hours, are obtained the presoma that particle diameter is 13 μm
C；
(6) presoma C 1000 DEG C of sintering, carbonization, screenings in the box Si-Mo rod or resistance wire furnace of nitrogen atmosphere are obtained final product
To the finished product that particle diameter is 16 μm.
According to 2 identical method assembled battery of embodiment and tested, its result is as shown in table 2.
1 embodiment 2-7 cell testing results table of table
As shown in Table 1：Lithium cell cathode material performance prepared by preparation method of the present invention is good, is obtained using the negative material
Lithium ion battery initial capacity it is big, in more than 650mAh/g, peak capacity reaches 920mAh/g to capacity；Coulombic efficiency exists
More than 85%, up to 89.0%；After 200 weeks, capability retention is more than 70%, and up to 86%, hold after circulation in 200 weeks
Amount is held in more than 540Ah/g；5C multiplying powers more than 95%, up to 99.5%.
As the theoretical capacity of silicon is up to 4200mAh/g, graphite theoretical capacity is only 372mAh/g, therefore silicon is in material
The contribution of how many pairs of percentage composition whole battery initial capacity it is maximum.Although by reducing silicon grain footpath, being used as substrate etc. with graphite
Means can reduce volumetric expansion, but these means all fundamentally can not definitely suppress what the volumetric expansion of silicon was caused to battery
Affect, therefore, when battery performance is considered, initial capacity, efficiency to be not only referred to, but also wants capacity after reference battery circulation
Situations such as conservation rate.Specifically, such as embodiment 2, although 920mAh/g of initial capacity 810mAh/g less than embodiment 4,
But the experiment parameter selected due to the embodiment 1 either ratio of silicon or other specification collocation is all relatively good, therefore 200
After Zhou Xunhuan, capacity remains 664mAh/g, and the capacity for being higher than embodiment 4 remains 644mAh/g, and high rate performance is also relatively good
Some.
For illustrating above-described embodiment situation, now change some of preparation scheme technique, other specification is constant and prepare
Comparative example's battery performance is contrasted with embodiment 1-2, to further illustrate the positive effect of the present invention, its result
See the table below 2.
2 embodiment 1-2 of table is contrasted with comparative example 1 and 2 cell testing results
Compared with embodiment 1-2, comparative example 1 for not adopting spray drying, but by the nano-silicon of equal proportion amount,
Graphite and the direct mechanical fusion of conductive agent, it is subsequently not resin-coated, only coat Colophonium once, finally sintering, screening obtains battery
Negative material.Compared with embodiment 1-2, comparative example 2 is only to remove the mechanical fusion in 3 steps, using common
Mechanical mix techniques, unclassified stores ratio and scheme do not change and prepare cell negative electrode material.As can be seen that 2 contrasts are real
Example is applied compared with embodiment 1-2, either capacity, coulombic efficiency or capacity keep first, conservation rate and multiplying power are all far below
Embodiment 1-2, cuts capacity and keeps being below 500mAh/g.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of spirit or essential attributes without departing substantially from the present invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit is required rather than described above is limited, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of description is only that those skilled in the art should for clarity
Using description as an entirety, the technical scheme in each embodiment can also Jing it is appropriately combined, form those skilled in the art
Understandable other embodiment.
Claims (15)
1. a kind of preparation method of lithium ion battery negative material, it is characterised in that comprise the following steps：
(1) silica flour and dispersant are carried out into wet ball grinding, obtains silicon slurry；
(2) after mixed homogeneously silicon slurry with graphite, conductive agent, it is spray-dried, is obtained near-spherical granule；
(3) near-spherical granule is carried out into mechanical fusion and obtains precursor A；
(4) mechanical fusion will be carried out after precursor A and resin VC batch mixings, then coated in cladding kettle, obtain precursor B；
(5) mechanical fusion will be carried out after precursor B and Colophonium VC batch mixings, then coated in cladding kettle, obtain presoma C；
(6) presoma C is sintered under an inert atmosphere, carbonization, screening obtain final product lithium ion battery negative material.
2. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that in step (1), institute
It is that silica flour is milled to D50 particle diameters for 50-350nm to state wet ball grinding；The dispersant is sodium carboxymethyl cellulose, polyvinyl alcohol
In one in or the two mixing, the 0.01-0.25% of the addition of dispersant for silicon slurry gross mass；The quality of silicon in silicon slurry
Concentration is 5-15%.
3. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that in step (1), institute
It is that silica flour is milled to D50 particle diameters for 150-250nm to state wet ball grinding.
4. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that silicon in step (2)
The consumption of slurry is silicon slurry, graphite, the 12-23% of conductive agent three's gross mass, and the consumption of the graphite is silicon slurry, stone
Ink, the 75-85% of conductive agent three's gross mass, the conductive agent consumption are silicon slurry, graphite, conductive agent three's gross mass
0.5-3.5%；The graphite is Delanium and/or native graphite, and particle diameter is 2～10 μm.
5. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that institute in step (2)
The consumption for stating silicon slurry is calculated with the quality of silica flour contained therein as standard, and the consumption of the silica flour is silica flour, graphite, leads
The 12-23% of electric agent three gross mass, the consumption of the graphite is silica flour, graphite, the 75-85% of conductive agent three's gross mass,
The conductive agent consumption is silica flour, graphite, the 0.5-3.5% of conductive agent three's gross mass；The graphite be Delanium and/or
Native graphite, particle diameter are 2～10 μm.
6. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that in step (3), melt
The conjunction time is 5-60min；The particle diameter of precursor A is 6-13 μm.
7. the preparation method of lithium ion battery negative material according to claim 5, it is characterised in that in step (3), melt
The conjunction time is 20-40min.
8. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that in step (4), institute
Resin is stated for phenolic resin, epoxy resin, one or more in politef, resin is 1 with the mass ratio of precursor A:
3-1:10；The time of fusion is 5-30min；The cladding is heat treated under an inert atmosphere, and heating-up temperature is 300-
700 DEG C, it is incubated 1-5 hours；The particle diameter of the precursor B is 8-15 μm.
9. the preparation method of lithium ion battery negative material according to claim 7, it is characterised in that in step (4), tree
Fat is 1 with the mass ratio of precursor A:5-1:10.
10. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that in step (5),
The Colophonium is the one kind in selected from coal tar pitch and petroleum asphalt, and the asphalt softening point is 120-300 DEG C, the matter of Colophonium and precursor B
Amount is than being 1:2-1:6；The time of fusion is 10-50min；The cladding is that heating-up temperature is 400-600 under an inert atmosphere
DEG C, it is incubated 2-6 hours；The particle diameter of the precursor C is 10-17 μm.
The preparation method of 11. lithium ion battery negative materials according to claim 9, it is characterised in that in step (5),
Colophonium is 1 with the mass ratio of precursor B:3-1:4.
The preparation method of 12. lithium ion battery negative materials according to claim 1, it is characterised in that in step (6),
Sintering, the temperature of carbonization are 900～1100 DEG C, and sintering, the time of carbonization are 6～10 hours, gained lithium ion battery after screening
Negative material particle diameter is 11-18 μm.
Lithium ion battery negative material obtained in a kind of 13. preparation methoies as described in any one of claim 1～11.
A kind of application of 14. lithium ion battery negative materials as claimed in claim 12 in lithium ion battery is prepared.
A kind of 15. lithium ion batteries comprising lithium ion battery negative material as claimed in claim 12.
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| CN107785560A (en) * | 2017-11-15 | 2018-03-09 | 国联汽车动力电池研究院有限责任公司 | A kind of high performance silicon carbon negative pole material and preparation method thereof |
| CN107863498A (en) * | 2017-09-20 | 2018-03-30 | 广东省稀有金属研究所 | A kind of preparation method of cathode material of lithium-ion power battery |
| CN109755517A (en) * | 2018-12-29 | 2019-05-14 | 陕西煤业化工技术研究院有限责任公司 | A kind of silicon-carbon composite anode material for lithium ion battery and preparation method thereof |
| CN110828779A (en) * | 2019-12-11 | 2020-02-21 | 东莞维科电池有限公司 | Lithium ion battery negative plate, preparation method thereof and lithium ion battery |
| CN110858642A (en) * | 2018-08-24 | 2020-03-03 | 中信国安盟固利动力科技有限公司 | Preparation method of silicon/graphite/solid electrolyte composite negative electrode material |
| CN111841383A (en) * | 2019-04-26 | 2020-10-30 | 宁德时代新能源科技股份有限公司 | Negative electrode material production equipment |
| CN112366315A (en) * | 2020-11-30 | 2021-02-12 | 河南开炭新材料设计研究院有限公司 | Production method of lithium battery negative electrode material |
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| CN113644252A (en) * | 2021-08-04 | 2021-11-12 | 西北工业大学 | Silicon-carbon negative electrode material and preparation method thereof |
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| CN107863498A (en) * | 2017-09-20 | 2018-03-30 | 广东省稀有金属研究所 | A kind of preparation method of cathode material of lithium-ion power battery |
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| CN110858642B (en) * | 2018-08-24 | 2021-12-28 | 荣盛盟固利新能源科技股份有限公司 | Preparation method of silicon/graphite/solid electrolyte composite negative electrode material |
| CN109755517A (en) * | 2018-12-29 | 2019-05-14 | 陕西煤业化工技术研究院有限责任公司 | A kind of silicon-carbon composite anode material for lithium ion battery and preparation method thereof |
| CN111841383A (en) * | 2019-04-26 | 2020-10-30 | 宁德时代新能源科技股份有限公司 | Negative electrode material production equipment |
| CN111841383B (en) * | 2019-04-26 | 2022-07-12 | 宁德时代新能源科技股份有限公司 | Negative electrode material production equipment |
| WO2021040932A1 (en) * | 2019-08-29 | 2021-03-04 | Novonix Battery Testing Services Inc. | Improved microgranulation methods and product particles therefrom |
| CN110828779A (en) * | 2019-12-11 | 2020-02-21 | 东莞维科电池有限公司 | Lithium ion battery negative plate, preparation method thereof and lithium ion battery |
| CN114122342A (en) * | 2020-08-31 | 2022-03-01 | 贝特瑞新材料集团股份有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
| CN112366315A (en) * | 2020-11-30 | 2021-02-12 | 河南开炭新材料设计研究院有限公司 | Production method of lithium battery negative electrode material |
| CN113644252A (en) * | 2021-08-04 | 2021-11-12 | 西北工业大学 | Silicon-carbon negative electrode material and preparation method thereof |
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Application publication date: 20170322 |