CN106558684A - A kind of compound negative material and preparation method thereof and battery - Google Patents
A kind of compound negative material and preparation method thereof and battery Download PDFInfo
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- CN106558684A CN106558684A CN201510638499.3A CN201510638499A CN106558684A CN 106558684 A CN106558684 A CN 106558684A CN 201510638499 A CN201510638499 A CN 201510638499A CN 106558684 A CN106558684 A CN 106558684A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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Abstract
The present invention relates to a kind of compound negative material, it is characterised in that the negative material includes inner nuclear layer and outer shell, and the material of the inner nuclear layer is at least one carbonaceous material in graphite, soft carbon and hard carbon；The outer shell contains amorphous carbon and formula LixCoSnyOzShown stannum cobalt lithium salts, wherein, 1<X≤2,1<Y≤2,4<z<6.Present invention also offers the preparation method of above-mentioned compound negative material, and battery of the negative pole containing above-mentioned compound negative material.The compound negative material of the present invention can overcome the volumetric expansion problem in charge and discharge process, so as to the negative pole that the compound negative material passed through using the present invention is formed, the battery of gained can be caused to have preferable cycle performance.
Description
Technical field
The present invention relates to a kind of compound negative material and preparation method thereof and battery.
Background technology
Prior art is mixed with the complex of Kong Jie's carbon ball and stannum cobalt using stannum cobalt and organic carbon source, system
Preparation Method includes：Stannum source solution is added dropwise in cobalt source solution, before being obtained using solution deposit
Body material；Precursor material is calcined under an inert atmosphere and obtains stannic acid cobalt nanometer particle group；By stannum
Sour cobalt nanometer particle group is placed in the saccharide solution of solubility, and carbon coating stannum is obtained by hydro-thermal carbon coating
Sour cobalt nanometer particle group；The carbon coating stannic acid cobalt nanometer particle is rolled into a ball calcining under an inert atmosphere to obtain
Carbon coating stannic acid cobalt nanometer particle group with meso-hole structure；The meso-hole structure prepared described in said method
The tin negative pole material porosity of carbon coating is less, and hole is less, can not alleviate negative material well and exist
Volumetric expansion problem in charge and discharge process, obtains preferably electricity circulation so as to cause gained battery to be difficult to
Performance, and the specific surface area of the tin negative pole material of meso-hole structure carbon coating is larger, and side reaction is more,
First charge-discharge efficiency is relatively low.
The content of the invention
It is an object of the invention to it is swollen to overcome existing tin negative pole material to there is volume in charge and discharge process
Swollen defect, causes gained battery to be difficult to obtain preferably electricity cycle performance, there is provided one kind can be compared with
Alleviate well volumetric expansion problem of the negative material in charge and discharge process, follow so as to obtain preferable electricity
Compound negative material of ring performance and preparation method thereof.
To achieve these goals, the present invention provides a kind of compound negative material, the negative material bag
Include inner nuclear layer and outer shell, the material of the inner nuclear layer be in graphite, soft carbon and hard carbon at least
A kind of carbonaceous material；The outer shell contains amorphous carbon and formula LixCoSnyOzShown stannum cobalt lithium
Salt, wherein, 1<X≤2,1<Y≤2,4<z<6.
Present invention also offers the preparation method of above-mentioned compound negative material, the method includes：
A cobalt organic compound, tin organic compound and carbon source material are mixed by (), obtain first
Mixture；
B first mixture is mixed by () with the material of inner nuclear layer, obtain the second mixture；
C second mixture, lithium-containing compound and precipitant are carried out being mixed to get the 3rd mixing by ()
Thing, and the 3rd mixture of gained is dried；
D the solid that step (c) is dried gained is carried out pyrolytic process by ().
The compound negative material of the present invention can overcome the volumetric expansion problem in charge and discharge process,
So as to the negative pole that the compound negative material passed through using the present invention is formed, the battery of gained can be caused
With preferable cycle performance.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
It is bright.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description,
It is used for explaining the present invention together with detailed description below, but does not constitute the limit to the present invention
System.In the accompanying drawings：
Fig. 1 is the field emission scanning electron microscope figure of the negative material obtained by embodiment 1.
Fig. 2 is the partial enlarged drawing of the field emission scanning electron microscope figure of the negative material obtained by embodiment 1.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of compound negative material, and the negative material includes inner nuclear layer and outer shell,
The material of the inner nuclear layer is at least one carbonaceous material in graphite, soft carbon and hard carbon；It is described
Outer shell contains amorphous carbon and formula LixCoSnyOzShown stannum cobalt lithium salts, wherein, 1<X≤2,
1<Y≤2,4<z<6.
According to the present invention, the negative material includes inner nuclear layer and outer shell, wherein, the material of inner nuclear layer
Expect at least one in graphite (natural or artificial can), soft carbon and hard carbon, outer shell
Formed by amorphous carbon and also contain formula LixCoSnyOzShown stannum cobalt lithium salts, such amorphous carbon
It is usually obtained by some carbon source materials (detailed description sees below) Jing high temperature cabonizations.Wherein, it is described outer
Contain formula Li in shellxCoSnyOzShown stannum cobalt lithium salts, so as to by be previously added elemental lithium and
Inactive cobalt element, preferably to avoid the expansion of negative material in charge and discharge process, improves battery
Cycle performance.
According to the present invention, to formula LixCoSnyOzThe content of shown stannum cobalt lithium salts has no particularly
Limit, as long as the expansion issues of negative material can be alleviated, under preferable case, with the shell
On the basis of the gross weight of layer, formula LixCoSnyOzThe content of shown stannum cobalt lithium salts is 70-90 weights
Amount %.
Wherein, to formula LixCoSnyOzThe granular size of shown stannum cobalt lithium salts has no special limit
It is fixed, can be present in the outer shell with arbitrary form, it is preferable that formula LixCoSnyOzInstitute
The stannum cobalt lithium salts for showing is the granule that particle diameter is 30-60nm.
According to the present invention, the outer shell can also the stannum containing other forms and cobalt compound, example
Such as can also the oxide containing stannum, the oxide of cobalt, lithium stannate, cobalt acid lithium, simple substance stannum and simple substance
The forms such as cobalt.
Preferably, in the outer shell, the weight ratio of cobalt element, tin element and carbon is 1：
2-6：1-3.It is highly preferred that the weight ratio of cobalt element and tin element is 1：2-4.
According to the present invention, the outer shell can also be containing other auxiliary agents, and the auxiliary agent is to increase
One kind or many in the CNT of strong outer shell stability and electric conductivity, acetylene black, Graphene etc.
Kind, the content of the auxiliary agent is 3-8 weight % (on the basis of the gross weight of outer shell).
According to the present invention, special limit is had no to the amount of the inner nuclear layer and outer shell of the negative material
It is fixed, as long as the negative material of the present invention can be obtained, there is preferably circulation in order to obtain
The negative material of performance, under preferable case, the weight ratio of the carbon of the outer shell and inner nuclear layer is
5-15：100.
According to the present invention, to the particle size of the compound negative material, there is no particular limitation, can
Think the conventional size in this area, it is preferable that the material of the inner nuclear layer is spherical graphite, the ball
Particle diameter distribution D50 of shape graphite is 8-18 μm, and (preferably particle diameter is 8-18 μm of spherical graphite as interior
Stratum nucleare).In the case where the weight of carbon of above-mentioned outer shell and inner nuclear layer ratio is met, the shell
The thickness of layer can be 0.2-1 μm.So as to particle diameter distribution D50 of the negative material is 8-20 μm.
According to the present invention, the compound negative material has preferable electric property, wherein, pass through
Button cell method of testing, the weight ratio capacity at 25 DEG C are 380-450mAh/g.Follow through 50 times
After ring, the conservation rate of weight ratio capacity can reach more than 80%, and conservation rate here is referred to through 50
The percentage ratio of weight ratio capacity and the weight ratio capacity for measuring first after secondary circulation.
According to the present invention, the relative crystallinity of the negative material is preferably 3-10.
According to the present invention, the negative material has higher spy in the range of 15-25 ° in 2 θ of the angle of diffraction
Diffraction maximum is levied, preferably the diffraction maximum relative intensity is 3-10%.
Present invention also offers the preparation method of above-mentioned compound negative material, the method includes：
A cobalt organic compound, tin organic compound and carbon source material are mixed by (), obtain first
Mixture；
B first mixture is mixed by () with the material of inner nuclear layer, obtain the second mixture；
C second mixture, lithium-containing compound and precipitant are carried out being mixed to get the 3rd mixing by ()
Thing, and the 3rd mixture of gained is dried；
D the solid that step (c) is dried gained is carried out pyrolytic process by ().
According to the present invention, by cobalt organic compound, tin organic compound and carbon source material in step (a)
Mixed to obtain the component needed for outer shell, to the cobalt organic compound, stannum organic compound
There is no particular limitation for thing, as long as the outer shell for enabling to the negative material of gained has formula
LixCoSnyOzShown stannum cobalt lithium salts.
Preferably, the cobalt organic compound is cobalt acetate and/or cobalt oxalate.
Preferably, the tin organic compound is tributyltin chloride, n-butyl alcohol stannum, ethanol stannum and different
One or more in propanol stannum.
According to the present invention, as described above the material of the inner nuclear layer be selected from graphite, soft carbon and
At least one carbonaceous material in hard carbon.
Preferably, the consumption of the cobalt organic compound, tin organic compound and carbon source material is caused,
In the outer shell of gained negative material, the weight ratio of cobalt element, tin element and carbon is 1：2-6：
1-3.Under the conditions of as meeting, such as relative to the carbonaceous material of 100 weight portions, with cobalt element
Meter the cobalt organic compound consumption be 1-10 weight portions (preferably 2-5 weight portions), Yi Xiyuan
The consumption of the tin organic compound of element meter is 10-50 weight portions (preferably 20-35 weight portions),
The consumption of the carbon source material is 10-20 weight portions.
It is highly preferred that in first mixture, the cobalt organic compound, tin organic compound and
The weight ratio of carbon source material is 1-3：6-12：1.
To the carbon source material, there is no particular limitation, as long as form outer shell being in a subsequent step
Can, under preferable case, the carbon source material be Colophonium (such as asphalt, coal tar pitch), sucrose,
One or more in glucose, starch, phenolic resin and epoxy resin.
According to the present invention, the mixing in step (a) can also be carried out in the presence of dispersants, described point
Powder can for example be ethanol etc..Under preferable case, such as relative to the cobalt organic compound of 100 weight portions
The gross weight of thing, tin organic compound and carbon source material, the consumption of the dispersant is 300-500 weight
Part.
According to the present invention, to the mixing condition in step (a), there is no particular limitation, as long as can be by
In above-mentioned material mix homogeneously, such as step (a), mixing be by the way of ball milling, its
Part includes：Rotating speed is 100-200rpm, and the time is 2-5h.
According to the present invention, the first mixture of gained can be loaded to graphite granule up by step (b),
There is the graphite of cobalt organic compound, tin organic compound and carbon source material so as to obtain area load
Grain, that is, obtain the second mixture.Wherein, the size of the graphite granule can be in wider scope
Change, wherein, the size of the graphite granule has been largely fixed the big of the negative material of gained
It is little.Under preferable case, the particle diameter of the graphite granule is 8-18 μm of Spherical graphite particles.
According to the present invention, second mixture, lithium-containing compound and precipitant are carried out by step (c)
Mixing, wherein it is possible to be mixed lithium-containing compound and precipitant with second mixture respectively
Close, it is also possible to which the mixed liquor of lithium-containing compound and precipitant is mixed with second mixture,
It is preferred that the mixed liquor of lithium-containing compound and precipitant is added dropwise to second mixture in the way of Deca
In mixed.
Preferably, the lithium-containing compound is the one kind or many in Lithium hydrate, lithium carbonate and Quilonorm (SKB)
Plant, more preferably Lithium hydrate.
Wherein, the mixed liquor of the lithium-containing compound and precipitant can be lithium-containing compound and precipitant
Ethanol solution, the mixed solution of aqueous solution or both, will lithium-containing compound and precipitant be added to
Obtained solution in ethanol.Wherein, the content of the lithium-containing compound be 0.1-1 weight %, precipitant
Content be 1-5 weight %.The precipitant is preferably ammonium hydrogen carbonate, ammonia, carbamide, sodium bicarbonate
With one or more in potassium bicarbonate.It is preferred that being mixed with Lithium hydrate in the form of the solution of precipitant
It is obtained in the mixed liquor of the two, for example, can adopts ammonium bicarbonate aqueous solution, the 8-16g/L of 15-35g/L
Ammonia, one or more in the aqueous solution of urea of 20-30g/L.
According to the present invention, the condition that the 3rd mixture of gained is dried by step (c) can be ability
The conventional drying condition in domain, as long as the solvent in the 3rd mixture is removed.Such as described drying
Temperature be 100-200 DEG C.
According to the present invention, it is by carbon source material point that the pyrolytic in step (d) processes main purpose
Solve as amorphous carbon simple substance, obtain the outer shell of negative material；The precipitate of cobalt element and tin element
Decompose, obtain formula LixCoSnyOzShown stannum cobalt lithium salts, and the oxidation of the oxide and stannum of cobalt
Thing, even simple substance stannum, cobalt etc. (are obtained by simple substance carbon reduction).Therefore, the present invention is to step (d)
Pyrolytic process step there is no particular limitation, as long as such purpose can be realized.Example
Such as, the pyrolytic is processed and is included：Temperature is 800-1100 DEG C, and the time is 3-10h.Preferable case
Under, in step (d), the pyrolytic is processed to be included first in air atmosphere, at 300-350 DEG C
Heat treated 6-12h, then under an inert atmosphere, heat treated 1-3h at 500-600 DEG C, then
Heat treated 2-5h at 800-1100 DEG C again.
Allow to after step (4) so that, on the basis of the gross weight of the outer shell, formula
LixCoSnyOzThe content of shown stannum cobalt lithium salts is 5-20 weight %.
Wherein, the air atmosphere can carry out adding in the way of directly under reaction system exposure, air is heavy
Heat, or the mode of air is passed through in reaction system, to this, there is no particular limitation.Wherein, it is lazy
Property atmosphere can be supplied by the conventional non-interactive air stripping that can provide inert atmosphere in this area, such as nitrogen
One or more in gas, argon, helium etc..
Present invention also offers a kind of battery, its negative pole contains above-described compound negative material.
According to the present invention, the positive pole, barrier film and nonaqueous electrolyte liquid to the battery is not particularly limited
System, it is possible to use all types of positive poles, barrier film and non-aqueous solution electrolysis used in lithium ion battery
Liquid, as long as the negative pole that the battery is adopted contains compound negative material provided by the present invention.Institute
The preparation method for stating negative pole for example can include the present invention using various methods commonly used in the art
The compound negative material of proposition, negative pole bonding are mixed with negative pole solvent, are coated and/or are filled in negative pole
On collector, negative electrode material layer is formed on negative current collector surface, be dried, roll or do not roll, i.e.,
The negative pole is obtained.Preferably, in the negative electrode material layer of the battery, it is compound that the present invention is provided
The content of type negative material is 85-95 weight %；The species and content of the negative pole bonding agent can be this
The conventional selection in field.For example, the negative pole bonding agent can selected from carboxymethyl cellulose (CMC),
Kynoar (PVDF), politef (PTFE), polyvinyl alcohol (PVA), butadiene-styrene rubber
(SBR) at least one and in the various modified or non-modified bonding agents such as TPO emulsion.It is general next
Say, according to the difference of negative pole bonding agent species used, with bearing that the present invention of 100 weight portions is provided
On the basis of the material of pole, the consumption of the negative pole bonding agent can be 0.01-10 weight portions, preferably
0.02-8 weight portions；The negative electrode material layer preferably also contains cathode conductive agent, the cathode conductive agent choosing
At least one from carbon black, nikel powder and copper powder, to increase negative conductive, the use of cathode conductive agent
Amount is known to the skilled person.
One of ordinary skill in the art can easily can be selected according to the teaching of prior art
Positive pole, barrier film and the nonaqueous electrolytic solution of lithium ion battery of the present invention are selected and prepare, and by described
Positive pole, the negative pole of the present invention, barrier film and nonaqueous electrolytic solution are obtained the lithium ion battery of the present invention.
The composition of the positive pole is known to those skilled in the art.In general, positive pole includes afflux
Body and coating and/or the positive electrode being filled on collector, the positive electrode include positive electrode active material
Matter, positive conductive agent and positive electrode binder.
The preparation method of the positive pole can adopt various methods commonly used in the art, for example, can include
Positive active material, positive conductive agent and positive electrode binder are mixed with negative pole solvent, is coated and/or is filled out
Fill on positive electrode collector, be dried, roll or do not roll, you can obtain the positive pole.
According to the present invention, the positive active material can adopt various positive-actives well known in the art
Material, such as LiCoO2、LiVPO4、LiCoAlO2、LiMnCoO2、LiCoxNiyMnzO2
(x+y+z=1), LiMn2O4、LiNiO2And LiFexM1-xPO4(M be Co, Ni, Mn,
At least one in 0.8≤x≤1).In the present invention, the consumption of the positive active material can be ability
The conventional amount used in domain.
The present invention is not particularly limited for the positive conductive agent in the positive electrode, can be ability
The conventional positive conductive agent in domain, for example, can be selected from carbon black, graphite, acetylene black, carbon fiber, carbon
At least one in nanotube, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder.The positive pole material
The consumption of the positive conductive agent in material can be the conventional amount used of this area.Usually, with 100 weight portions
On the basis of positive active material, the content of the positive conductive agent of positive pole can be 0.5-15 weight portions, excellent
Elect 1-10 weight portions as.
Positive electrode binder in the positive electrode can be various positive electrode binders commonly used in the art,
Can for example be selected from polyvinylidene fluoride, politef, (fluorine-containing) polyacrylate, (fluorine-containing)
Polyurethane, (fluorine-containing) epoxy resin, butadiene-styrene rubber, poly- methylcellulose, poly- sodium carboxymethylcellulose pyce,
At least one of hydroxypropyl methyl cellulose, POLYPROPYLENE GLYCOL and butadiene-styrene rubber (SBR).In general,
According to the difference of adhesive therefor species, on the basis of 100 weight portion positive active materials, the positive pole
The content of the binding agent in material can be 0.01-10 weight portions, preferably 0.02-7 weight portions
It can be various solvents commonly used in the art to prepare the positive pole solvent used during positive pole, for example may be used
Think selected from N-Methyl pyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide,
At least one in tetrahydrofuran and water and alcohol series solvent.
The species of the collector in the positive pole and negative pole is known to those skilled in the art, example
Any one in aluminium foil, Copper Foil, Punching steel strip can be such as selected from.
The barrier film is arranged between positive pole and negative pole, with electrical insulation capability and liquid retainability energy.
The barrier film can be various barrier films used in lithium ion battery, such as polyolefin micro porous polyolefin membrane,
Polyethylene felt, glass mat or ultra-fine fibre glass paper.The position of the barrier film, property and species
It is known to those skilled in the art.
The nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvent, to which without special
Limit, it is possible to use the conventional nonaqueous electrolytic solution in this area.Such as electrolyte lithium salt can be selected from six
Lithium fluophosphate (LiPF6), lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine aluminum
At least one in sour lithium and fluorohydrocarbon base Sulfonic Lithium.Nonaqueous solvent can select chain acid esters and ring-type acid
Ester mixed solution, wherein chain acid esters can be selected from dimethyl carbonate (DMC), diethyl carbonate
(DEC), Ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC)
And other fluorine-containing, sulfur-bearings or at least one in the chain organosilane ester containing unsaturated bond, ring-type acid
Ester can be selected from ethylene carbonate (EC), Allyl carbonate (PC), vinylene carbonate (VC),
Gamma-butyrolacton (γ-BL), sultone and other fluorine-containing, sulfur-bearings or the ring-type organic ester containing unsaturated bond
At least one of apoplexy due to endogenous wind.Generally, the injection rate of nonaqueous electrolytic solution is 1.5-5.5 gram/ampere-hour, dense
Spend rub for 0.1-2.0/liter.
The preparation method of the battery is known to the skilled person, in general, by membrane layer
Positive pole and negative pole winding are separated to form electrode group, the electrode group for obtaining and nonaqueous electrolytic solution are sealed in
In battery case, you can the battery of present invention offer is provided.
As above-mentioned battery employs the compound negative material of present invention offer, preferably can alleviate
The expansion issues of negative material, so that the battery of gained has preferable cycle performance.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example,
In outer shell, the weight ratio of cobalt element, tin element and carbon is measured by ICP/AAS
's.
The thickness of outer shell is measured by TG-DSC/TEM.
The relative crystallinity of negative material is measured by XRD method.
Particle diameter distribution D50 of negative material is measured by PSA methods.
The weight ratio of the carbon of outer shell and inner nuclear layer is measured by TG-DSC methods.
LixCoSnyOzShown stannum cobalt lithium salts is measured by XRD, ICP/AAS method.
Embodiment 1
The present embodiment is used to illustrate porous nucleocapsid structure negative material of the present invention and preparation method thereof.
A () is by the cobalt acetate of 13g, the tributyltin chloride of 80g, 10g coal tar pitchs (purchased from upper
Hai Dingyang Refractory Co., ltds) and 400g ethanol be added in ball grinder with the rotating speed ball of 150rpm
Mill 3h, obtains the first mixture；
(2) be subsequently adding 80g natural spherical plumbago granule (particle diameter distribution D50 be 11.2 μm, purchase
From the calm and peaceful grand new energy materialses company limited NG-21 trades mark in Qingdao), and in the rotating speed ball milling of 50rpm
1h, obtains the second mixture；
(3) by the ethanol solution containing Lithium hydrate and ammonia, (450g, Lithium hydrate content is
2.5g, NH3Content is 7g) to be added dropwise in the second mixture, and uniformly mix, then by gained
3rd mixture is dried at 150 DEG C, obtains solid；
(4) by solid obtained by step (3) in air atmosphere heat treatment 8h, Ran Hou at 300 DEG C
In nitrogen atmosphere, 5 DEG C/min is warmed up to 500 DEG C, is incubated 2h；It is warmed up to 10 DEG C/min afterwards
1050 DEG C, 4h is incubated, compound negative material CA1 is obtained.The compound negative material CA1's
Particle diameter distribution D50 is 11.4 μm, and the thickness of outer shell is 0.2 μm, and BET test results show and compare table
Area is 6mm2/ g, relative crystallinity are diffraction maximums of 5, the XRD angles of diffraction, 2 θ in 15-25 ° of scope
Relative intensity is 5%, and the weight ratio of the carbon of outer shell and inner nuclear layer is 3：10, in outer shell,
The weight ratio of cobalt element, tin element and carbon is 1：4：1, on the basis of the gross weight of outer shell,
LixCoSnyOzThe content of shown stannum cobalt lithium salts be 83 amounts % (x be 1, y be 2, z be 5.5).
Embodiment 2
The present embodiment is used to illustrate porous nucleocapsid structure negative material of the present invention and preparation method thereof.
Method according to embodiment 1, except for the difference that：
In step (1), Shenzhen Puli Chemical Co., Ltd. RS-619 (is purchased from using the phenolic resin of 10g
The trade mark) replace coal tar pitch, and add and have the carbon nano tube paste of 10g (content of carbon nanotubes is 5
Weight %, purchased from the Tian Nai materials Science and Technology Ltd. LB200 trades mark)；
In step (3), Lithium hydrate is replaced using the lithium acetate of 4.3g；
In step (4), heat treated 10h at 300 DEG C, protects after being warming up to 1050 DEG C in air atmosphere
Warm 3h.
So as to obtain compound negative material CA2.The particle diameter distribution of the compound negative material CA2
D50 is 11.5 μm, and the thickness of outer shell is 0.3 μm, and relative crystallinity is 6, the XRD angles of diffraction, 2 θ
It is that 6%, BET test results show that specific surface area is in the diffraction maximum relative intensity of 15-25 ° of scope
8mm2The weight ratio of the carbon of/g, outer shell and inner nuclear layer is 3：10, in outer shell, cobalt element,
The weight ratio of tin element and carbon is 1：4：1, on the basis of the gross weight of outer shell,
LixCoSnyOzThe content of shown stannum cobalt lithium salts be 81 amounts % (x be 1.1, y be 2, z be 5.55).
Embodiment 3
The present embodiment is used to illustrate porous nucleocapsid structure negative material of the present invention and preparation method thereof.
Method according to embodiment 1, except for the difference that：
In step (1), the consumption of coal tar pitch is 8g, and adds 0.5g acetylene blacks (purchased from middle rubber
Company of carbon black industry studying and designing institute of the group V7 trades mark)；
In step (3), Lithium hydrate is replaced using the lithium acetate of 5.2g；
In step (4), heat treated 12h at 300 DEG C, protects after being warming up to 1050 DEG C in air atmosphere
Warm 5h.
So as to obtain compound negative material CA3.The particle diameter distribution of the compound negative material CA3
D50 is 11.4 μm, and the thickness of outer shell is 0.2 μm, and relative crystallinity is 8, the XRD angles of diffraction, 2 θ
It is that 8%, BET test results show that specific surface area is in the diffraction maximum relative intensity of 15-25 ° of scope
7mm2The weight ratio of the carbon of/g, outer shell and inner nuclear layer is 3：10, in outer shell, cobalt element,
The weight ratio of tin element and carbon is 1：4：1, on the basis of the gross weight of outer shell,
LixCoSnyOzThe content of shown stannum cobalt lithium salts be 80 weight % (x be 1.2, y be 2, z be 5.6).
Comparative example 1
32.4g carbamide is weighed, in easy 85 DEG C of water, the solution for standby that pH is 10 is configured to.
Weigh spherical natural graphite 100g, 23.6g butter of tin and 100g rustless steel pellets be placed in it is stainless
Seal in cylinder of steel, under 200rpm rotating speeds, ball milling was slowly added to urea liquid after 60 minutes,
It is stirred continuously during addition, mixing speed is 300rpm.Reaction temperature is 85 DEG C, reaction
Time is 4h, after reaction terminates, filters, washs, dries, obtains precursor A.Weigh 10g
Medium temperature coal pitch is dissolved in tetrahydrofuran, is configured to 5% clad solution 400ml, standby.
Precursor A is put into into impregnation process in cold primer-oil, with 300rpm stir process 1h.Then dry
Dry tetrahydrofuran, is stirred continuously pelletize during drying.Then in nitrogen atmosphere, with
5 DEG C/min is warming up to 400 DEG C, is incubated 2h, is warming up to 1000 DEG C with 10 DEG C/min afterwards, protects
Warm 2h.Naturally cool to room temperature and obtain negative material CB1, its particle diameter distribution D50 is 13 μm,
The thickness of outer shell is 0.3 μm, and relative crystallinity is 8, the XRD angles of diffraction, 2 θ in 15-25 ° of scope
Diffraction maximum relative intensity is that 8%, BET test results show that specific surface area is 12mm2/ g, outer shell and
The weight ratio of the carbon of inner nuclear layer is 0.7：10, there is no LixCoSnyOzShown stannum cobalt lithium
Salt.
Test case 1
Each negative material in above example 1-3 and comparative example 1 is prepared as follows into into button
Battery：The negative material of above-described embodiment and comparative example is pressed into following proportioning negative material：Acetylene black：
CMC：SBR=100：2：1.5：Tabletting after 2.5 ratio mix homogeneously, 120 DEG C of vacuum drying 24h
Obtain testing pole piece；It is that, to electrode, celgard2400 polypropylene porous films are barrier film with metal lithium sheet,
1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed solution (volume ratio
For=1：1) for electrolyte full of argon glove box in assemble, prepare battery S1-S3 and
DS1。
Method of testing：
Held by the embedding lithium capacity of above-mentioned each battery, de- lithium are measured using button cell method
Amount, and circulate the embedding lithium capacity after 50 times, de- lithium capacity.
Wherein, specific discharge capacity includes the de- lithium capacity of the embedding lithium capacity of mass ratio, mass ratio, the mass ratio
The computational methods of the de- lithium capacity of embedding lithium capacity, mass ratio be according to embedding lithium capacity and de- lithium calculation of capacity and
, it is the ratio for surveying removal lithium embedded capacity and the activity substance content of the actual attachment of pole piece.
Which is the results are shown in Table shown in 1：
Table 1
Note：Efficiency refers to efficiency for charge-discharge, is the percentage ratio of de- lithium capacity and embedding lithium capacity.Capability retention is referred to and is followed
Ring takes off lithium specific discharge capacity 50 times and the percentage ratio for taking off lithium specific discharge capacity first afterwards.
As shown in Table 1, using battery S1-S4 circulations made by the compound negative material for providing of the invention
The minimum 338mAh/g of embedding lithium capacity after 50 times, circulation take off lithium capacity minimum 334 50 times afterwards
The 285mAh/g and 282mAh/g of mAh/g, significantly larger than DS1, after circulating 50 times, capacity keeps
Rate is more than 80%, it is seen then that battery made by the compound negative material that the present invention is provided has excellent
Cycle performance.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the range of the technology design of the present invention, can be to the skill of the present invention
Art scheme carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as
Its thought without prejudice to the present invention, which should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of compound negative material, it is characterised in that the negative material includes inner nuclear layer and shell
Layer, the material of the inner nuclear layer is at least one carbonaceous material in graphite, soft carbon and hard carbon；Institute
State outer shell and contain amorphous carbon and formula LixCoSnyOzShown stannum cobalt lithium salts, wherein, 1<X≤2,
1<Y≤2,4<z<6.
2. negative material according to claim 1, wherein, the gross weight with the outer shell is
Benchmark, formula LixCoSnyOzThe content of shown stannum cobalt lithium salts is 70-90 weight %, it is preferable that described
Formula LixCoSnyOzShown stannum cobalt lithium salts is the granule that particle diameter is 30-60nm；
Preferably, the weight ratio of the carbon of the outer shell and inner nuclear layer is 5-15：100.
3. negative material according to claim 1 and 2, wherein, the outer shell also contains stannum
Oxide, the oxide of cobalt, lithium stannate, cobalt acid lithium, the one kind or many in simple substance stannum and simple substance cobalt
Kind, in the outer shell, the weight ratio of cobalt element, tin element and carbon is 1：2-6：1-3.
4. the negative material according to any one in claim 1-3, wherein, the inner nuclear layer
Material be spherical graphite, particle diameter distribution D50 of the spherical graphite is 8-18 μm.
5. the negative material according to any one in claim 1-4, wherein, the outer shell
In also contain auxiliary agent, the one kind or many of the auxiliary agent in CNT, acetylene black and Graphene
Kind, on the basis of the gross weight of the outer shell, the content of the auxiliary agent is 3-8 weight %.
6. the negative material according to any one in claim 1-5, wherein, the negative pole material
The relative crystallinity of material is 3-10.
7. the negative material according to any one in claim 1-6, wherein, the negative pole material
Material 2 θ of the angle of diffraction is 3-10% in the diffraction maximum relative intensity of 15-25 ° of scope.
8. the negative material according to any one in claim 1-7, wherein, the negative pole material
Particle diameter distribution D50 of material is 8-20 μm.
9. the preparation method of the compound negative material in a kind of claim 1-8 described in any one,
The method includes：
A cobalt organic compound, tin organic compound and carbon source material are mixed by (), obtain first
Mixture；
B first mixture is mixed by () with the material of inner nuclear layer, obtain the second mixture；
C second mixture, lithium-containing compound and precipitant are carried out being mixed to get the 3rd mixing by ()
Thing, and the 3rd mixture of gained is dried；
D the solid that step (c) is dried gained is carried out pyrolytic process by ().
10. method according to claim 9, wherein, in step (a), the cobalt organises
Compound is cobalt acetate and/or cobalt oxalate；
Preferably, the tin organic compound is tributyltin chloride, n-butyl alcohol stannum, ethanol stannum and different
One or more in propanol stannum；
Preferably, the lithium-containing compound is the one kind or many in Lithium hydrate, lithium carbonate and Quilonorm (SKB)
Kind.
11. methods according to claim 9 or 10, wherein, in step (a), mixing is to adopt
With the mode of ball milling, its condition includes：Rotating speed is 50-250rpm, and the time is 2-10h；
Preferably, in step (c), the condition of pyrolytic process includes：First in air atmosphere,
Heat treated 6-12h at 300-350 DEG C, then under an inert atmosphere, at heating at 500-600 DEG C
Reason 1-3h, then heat treated 2-5h at 800-1100 DEG C again.
A kind of 12. batteries, its negative pole contain the compound negative pole in claim 1-8 described in any one
Material.
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| CN108682804A (en) * | 2018-04-25 | 2018-10-19 | 福建翔丰华新能源材料有限公司 | A kind of hard carbon cladding soft carbon is used as the preparation method of lithium ion battery negative material |
| CN114420939A (en) * | 2022-03-31 | 2022-04-29 | 河北坤天新能源科技有限公司 | High-rate spherical hard carbon composite material and preparation method and application thereof |
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| CN102082262A (en) * | 2010-12-31 | 2011-06-01 | 上海交通大学 | Method for preparing nano-carbon coated lithium battery anode material |
| CN102544444A (en) * | 2010-12-29 | 2012-07-04 | 比亚迪股份有限公司 | Preparation method for lithium ion battery anode active material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102544444A (en) * | 2010-12-29 | 2012-07-04 | 比亚迪股份有限公司 | Preparation method for lithium ion battery anode active material |
| CN102082262A (en) * | 2010-12-31 | 2011-06-01 | 上海交通大学 | Method for preparing nano-carbon coated lithium battery anode material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108682804A (en) * | 2018-04-25 | 2018-10-19 | 福建翔丰华新能源材料有限公司 | A kind of hard carbon cladding soft carbon is used as the preparation method of lithium ion battery negative material |
| CN108682804B (en) * | 2018-04-25 | 2021-05-25 | 深圳市翔丰华科技股份有限公司 | Preparation method of lithium ion battery cathode material with hard carbon-coated soft carbon |
| CN114420939A (en) * | 2022-03-31 | 2022-04-29 | 河北坤天新能源科技有限公司 | High-rate spherical hard carbon composite material and preparation method and application thereof |
| CN114420939B (en) * | 2022-03-31 | 2022-06-21 | 河北坤天新能源股份有限公司 | High-rate spherical hard carbon composite material and preparation method and application thereof |
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