CN100414747C - Composite carbon negative electrode material of lithium ion power battery and its preparation method - Google Patents
Composite carbon negative electrode material of lithium ion power battery and its preparation method Download PDFInfo
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Abstract
The present invention discloses compound carbon negative pole materials of a lithium ion power battery and a preparation method thereof. A technical problem to be solved is to improve the big magnification discharge performance of the battery. Materials of the present invention are compound graphite particles which are combined or joined through agglomerant and are spherical or are similar to sphericity, and the surfaces of the compound graphite particles are dispersed with additive. The compound graphite particles comprise a weight ratio: the mixing of natural graphite powder, synthetic graphite powder or the natural graphite powder and the synthetic graphite powder, the additive occupying 0.1 to 5 percent of the weight of the graphite powder and the adhesive occupying 1 to 50 percent of the weight of the graphite powder. The preparation method of the present invention comprises: mixing granulation, calcination, impregnation, carbonization and graphitization treatment and pulverization. Compared with the prior art, the additive of the present invention is uniformly dispersed at the surface of the natural graphite or the synthetic graphite particles, the reversible specific capacity of negative pole materials of graphite is bigger than 350 mAh/g, coulomb efficiency circulated for the first time is bigger than 94 percent, and the content maintenance rate of 500 times of circulation is bigger than 80 percent. The present invention has the advantages of good lithium inserting and shedding capacity and stable circulation.
Description
Technical field
The present invention relates to a kind of cell negative electrode material and preparation method thereof, particularly composite graphite negative electrode material of a kind of lithium-ion-power cell and preparation method thereof.
Background technology
Since nineteen ninety Japan Sony company take the lead in succeeding in developing lithium ion battery and with its commercialization since, lithium ion battery has obtained fast development.Nowadays lithium ion battery has been widely used in civilian and military every field.Along with the continuous progress of science and technology, people have proposed more higher requirements to the performance of battery: the miniaturization of electronic equipment and individualized development need battery to have the specific energy output of littler volume and Geng Gao; The Aero-Space energy requires battery to have cycle life, better the security performance of low temperature charge-discharge performance and Geng Gao; Electric automobile needs the battery of big capacity, low cost, high stability and security performance.Succeeding in developing of lithium ion battery, should at first give the credit to electrode material, the particularly breakthrough of carbon negative pole material, in numerous material with carbon elements, graphitized carbon material is owing to have good layer structure, be very suitable for the embedding of lithium ion and take off embedding, the graphite of formation-lithium intercalation compound Li-GIC has higher specific capacity, near LiC
6Theoretical specific capacity 372mAh/g; Have favorable charge-discharge voltage platform and lower doff lithium current potential simultaneously, with the positive electrode that the lithium source is provided, as LiCoO
2, LiNiO
2And LiMn
2O
4Better etc. matching, as to be formed battery average voltage height, discharge is steady, and therefore the commercialization lithium ion battery adopts the graphite-like material with carbon element as negative material in a large number at present.
But, graphite material is because the degree of graphitization height, has height-oriented graphite laminate structure, relatively poor with the compatibility of organic solvent, common embedding, the graphite layers that lithium and organic solvent can take place when first charge-discharge peeled off, graphite granule bursts apart and efflorescence, causes electrode structure destruction, charge and discharge cycles to reduce; Because the laminated structure of graphite only allows lithium ion to embed along the border of graphite crystal and deviates from, and response area is little, the evolving path is long, generally is not suitable for high current charge-discharge in addition.Be easy to form sheet-like particle in the crushing process of graphite cathode material when powder preparing in addition with big draw ratio, form in the roll-in process of sheet-like particle when electrode preparation and be parallel to aligning of collector, lithium ion enters and deviates from graphite crystal and causes that the c direction of principal axis of graphite produces big strain when inner in the repeated charge process, cause electrode structure to destroy, influenced cycle performance, and the result that exfoliated graphite particles aligns also can cause lithium ion to enter from the side of graphite crystal and the resistance deviate from strengthens the fast charging and discharging performance variation.And, because the graphite crystal of sheet-like particle has bigger specific area with spherical comparing with the blocky graphite particle, therefore the negative material as lithium ion battery has bigger irreversible capacity in the first charge-discharge process, and the associativity of graphite powder and collector body is relatively poor, need to add a large amount of adhesives, increased the internal resistance of cell, reduced discharge capacity, fast charging and discharging performance and cycle performance worsen.
Summary of the invention
The purpose of this invention is to provide a kind of composite carbon negative electrode material of lithium ion power battery and preparation method thereof, the technical problem that solve is to improve the big multiplying power discharging property of battery, and tool has excellent fast charging and discharging performance and good cycle performance concurrently.
The present invention is by the following technical solutions: a kind of composite carbon negative electrode material of lithium ion power battery, described composite carbon negative electrode material of lithium ion power battery is the composite graphite particles by binding agent combination or combination, spherical in shape or class is spherical, the composite graphite particles surface is dispersed with additive; The weight ratio that composite graphite particles comprises is: natural graphite powder, graphous graphite powder or natural graphite powder mix with graphous graphite powder, account for the additive of graphite powder weight 0.1～5%, account for the binding agent of graphite powder weight 1～50%.
The average grain diameter of composite graphite particles of the present invention is 5～60 μ m, draw ratio between 1.5～4, specific area 1.0～4.0m
2/ g, tap density 0.7～1.5g/cm
3, crystal layer spacing d
002Between 0.335～0.340nm.
The crystalline size that composite graphite particles of the present invention has on the c of graphite crystal direction of principal axis is 50～150nm, is 50～100nm at the crystalline size of crystal basal plane orientation.
Additive of the present invention is conductive black, acetylene black, gas-phase growth of carbon fibre, carbon nano-tube or nano-sized carbon microballoon.
Binding agent of the present invention be pitch, tar or resin any, two or three mixing.
A kind of preparation method of composite carbon negative electrode material of lithium ion power battery, may further comprise the steps: one, be with granularity 0.1 μ m to 40 μ m, fixed carbon content 〉=94% graphite powder, account for graphite powder weight 0.1～5% additive, account for the binding agent of graphite powder weight 1～50%, mixing granulation; Two, with mixed pellet extrusion modling, its density is 1.6～1.75g/cm after the moulding
3, roasting afterwards, dipping; Three, molding mass is carried out graphitization processing or carbonization and graphitization processing, heating is 450 ℃ to 3000 ℃ in protective gas, is incubated 1 to 10 hour, reduces to room temperature then; Four, above-mentioned complex carbon material is pulverized, average grain diameter is 5～60 μ m.
Graphite powder of the present invention is one or more mixing in natural flake graphite, micro crystal graphite or the Delanium.
Additive of the present invention is conductive black, acetylene black, gas-phase growth of carbon fibre VGCF, carbon nano-tube or nano-sized carbon microballoon.
Binding agent of the present invention is a kind of or above-mentioned two or three mixture in pitch, tar or the resin.
When binding agent of the present invention was pitch and tar, the temperature of mixing granulation is chosen in 70～300 ℃ carried out, and when binding agent used resin, the temperature of mixing granulation was chosen in 20～100 ℃ and carries out.
A kind of preparation method of composite carbon negative electrode material of lithium ion power battery, may further comprise the steps: one, be with granularity 0.1 μ m to 40 μ m, fixed carbon content 〉=94% graphite powder, account for graphite powder weight 0.1～5% additive, account for the binding agent of graphite powder weight 1～50%, mixing granulation; Two, mixed pellet is carried out low-temperature carbonization and handle, heating is 450 ℃ to 1300 ℃ in protective gas, is incubated 1 to 10 hour, reduces to room temperature then; Three, above-mentioned complex carbon material is pulverized, average grain diameter is 5～60 μ m.
The present invention compared with prior art, composite carbon negative electrode material of lithium ion power battery is by natural graphite powder, graphous graphite powder, additive is by the composite graphite particles of binding agent combination or combination, additive is dispersed in the surface of native graphite or Delanium particle, the graphite cathode material reversible specific capacity is greater than 350mAh/g, coulombic efficiency circulate first greater than 94%, circulate 500 capability retentions greater than 80%, has good embedding, take off lithium ability and cyclical stability, preparation technology is simple, easy operating, with low cost, be applicable to lithium-ion-power cell, all kinds of portable device, electric tool, the electric vehicle lithium ion battery negative material.
Description of drawings:
Fig. 1 is the electromicroscopic photograph before the graphite powder of the embodiment of the invention 1 is handled.
Fig. 2 is the electromicroscopic photograph of the composite carbon negative electrode material of lithium ion power battery of the embodiment of the invention 1.
Fig. 3 is an XRD figure before the graphite powder of the embodiment of the invention 1 is handled.
Fig. 4 is the XRD figure of the composite carbon negative electrode material of lithium ion power battery of the embodiment of the invention 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
The secondary composite graphite particles that composite carbon negative electrode material of lithium ion power battery of the present invention is made up of by binding agent natural graphite powder, graphous graphite powder or natural graphite powder and graphous graphite powder evenly is dispersed with additive on the surface of native graphite or Delanium particle; The weight ratio that its composite graphite particles comprises is: natural graphite powder, graphous graphite powder or natural graphite powder mix with graphous graphite powder, account for the additive of graphite powder weight 0.1～5%, account for the binding agent of graphite powder weight 1～50%; The average grain diameter of composite graphite particles is 5～60 μ m, draw ratio between 1.5～4, specific area 1.0～4.0m
2/ g, tap density 0.7～1.5g/cm
3, crystal layer spacing d
002Between 0.335～0.340nm, the crystalline size on the c of graphite crystal direction of principal axis is 50～150nm, is 50～100nm at the crystalline size of crystal basal plane orientation.Additive is conductive black, acetylene black, gas-phase growth of carbon fibre VGCF, carbon nano-tube or nano-sized carbon microballoon.Binding agent be pitch, tar or resin any, two or three mixing.
The preparation method of composite carbon negative electrode material of lithium ion power battery of the present invention, may further comprise the steps: one, be with granularity 0.1 μ m to 40 μ m, fixed carbon content 〉=94% graphite powder, account for graphite powder weight 0.1～5% additive, account for the binding agent of graphite powder weight 1～50%, mixing granulation, add graphite powder, doping more earlier, mix the back adding additives; Two, with mixed pellet extrusion modling, its density is 1.6～1.75g/cm after the moulding
3, roasting afterwards, dipping adopt conventional graphite electrode roasting, impregnation technology, and the stage heating mode carries out roasting, 130 ℃～1300 ℃ of sintering temperatures, 1.3～10 ℃/h of programming rate, roasting time 320h～420h; The heated bitumen that in impregnation tank, adds 160 ℃～180 ℃ during dipping, the submergence goods, pressurization 1.18～2.5MPa keeps 2～4h, and is the same through roasting once more, dip parameters when requiring extrudate density higher; Three, molding mass is carried out carbonization treatment or graphitization processing, heating is 450 ℃ to 3000 ℃ in protective gas, is incubated 1 to 10 hour, reduces to room temperature then; Four, above-mentioned complex carbon material is pulverized.
The preparation method's of composite carbon negative electrode material of lithium ion power battery of the present invention graphite powder is one or more mixing in natural flake graphite, natural micro crystal graphite and the Delanium; The cooperation ratio of graphite powder is natural graphite powder: graphous graphite powder=0～100: 100～0.That is be to use natural graphite powder or graphous graphite powder, perhaps the two mixes in certain proportion.
Protective gas is nitrogen, argon gas, vacuum or reducibility gas, and tunnel cave well-known to those skilled in the art or graphitizing furnace are adopted in heat treatment.
As shown in Figure 1, it is irregularly shaped to be bulk, flakey etc. before graphite microparticles of the present invention is handled; As shown in Figure 2, graphite microparticles is spherical in shape or class is spherical after bonding granulation and heat treatment, the specific area of material reduces, tap density improves, bigger change has also taken place in the crystal structure of graphite, as shown in Figure 3, there was the diffraction maximum of the rhomboidan of graphite in graphite powder of the present invention about the angle of diffraction 43.3 degree and 46.0 degree before handling, illustrate that graphite powder is six sides phase and rhombus mixture mutually; As shown in Figure 4, composite carbon negative electrode material of lithium ion power battery rhombus phase diffraction maximum of the present invention disappears, and the rhombus inversion of phases is six more stable side's phases.Because the surface has coated one deck non-graphitic carbon material, the diffraction peak intensity of complex carbon material weakens, diffraction maximum broadening, d in the crystal structure
002Value has increase slightly.
Composite carbon negative electrode material of lithium ion power battery of the present invention is formed the complex carbon material that coating layer is formed jointly by sphere or class spherical graphite basis material and surface coated one deck thereof by binding agent pyrolytic carbon and additive.Above-mentioned basis material is mixed in certain proportion by natural graphite powder or graphous graphite powder or the two, account for the additive pyrolytic carbon of graphite powder weight 0.1～5% and account for the binding agent of graphite powder weight 1～50%, evenly be coated in conjunction with after substrate material surface, the two mutual group cost is applicable to the composite carbon negative electrode material of lithium ion power battery of lithium-ion-power cell.
As shown in Figure 2, composite carbon negative electrode material of lithium ion power battery of the present invention is by a plurality of exfoliated graphite particles combinations or is combined together to form second particle, the synusia of each graphite microcrystal of granule interior is random alignment each other, constitute non-ly between each crystal face be parallel to each other, microstructure that non-directional is arranged.Described exfoliated graphite particles is meant that coating of particles is the particle with a major axis and a minor axis, and promptly its shape is not desirable sphere.Comprise flakey, the laminar or irregular shape of column.Above-mentioned each second particle inside comprises a plurality of graphite microcrystals, and these graphite microcrystals are random alignment each other, non-being arranged parallel to each other between the therefore whole temper carbon granule interior graphite aspect.
Above-mentioned said " a plurality of exfoliated graphite particles make up or are combined together to form second particle ", " combination " is meant the state that combines by the binding agent intermediate medium between the graphite particulate; " combination " is meant the state that flocks together owing to shape, molecular separating force and capillary factor between the particle, reaches between the particle not by the intermediate medium combination.Obviously, from the viewpoint of mechanical strength, the particle that combines is more excellent selection.
The average grain diameter of composite carbon negative electrode material of lithium ion power battery of the present invention is 5～60 μ m, the average grain diameter size of single graphite granule is at 0.1～40 μ m, be below 2/3 of second particle size that single graphite granule is formed, the graphite granule quantity that is together with each other is more than 3; Unlikely excessive and influence charge-discharge performance for individual particle is combined second particle size that the back forms, the graphite granule quantity that is together with each other should be below 2175.Above-mentioned average grain diameter adopts Britain Malvem Mastersizer 2000 laser particle size analyzers to measure.
Composite carbon negative electrode material of lithium ion power battery of the present invention has the draw ratio of particle between 1.5～4.Draw ratio adopts following method definition, if the major axis dimension of individual particle is a, minor axis dimension is b, and then draw ratio is a/b, and the present invention adopts NEC JEOLJSM-6380LV ESEM, U.S. Millitrac particle image analysis-e/or determining.Less than 1.5 o'clock, the contact area between the particle reduced, and has reduced conductivity in said draw ratio; Greater than 4 o'clock, the degree of combination reduced between the particle in the draw ratio of particle, can worsen the fast charging and discharging performance of material equally.
Composite carbon negative electrode material of lithium ion power battery of the present invention also has 1.0～4.0m
2The specific area of/g adopts the BET method of nitrogen adsorption to measure.Specific area by adjusting material can be improved the fast charging and discharging performance and the cycle performance of battery, and reduce the irreversible capacity in the first charge-discharge process in suitable scope.Described specific area is greater than 4.0m
2During/g, irreversible capacity loss strengthens in the cyclic process first, and worsens drawing abillity, need add a large amount of binding agents when negative pole prepares; And specific area is less than 1.0m
2/ g, the fast charging and discharging performance of battery and cycle performance can be adversely affected.The tap density of composite carbon negative electrode material of lithium ion power battery of the present invention adopts Quantachrome AutoTap tap density instrument to measure.When the tap density of powder less than 0.7g/cm
3The time, material has lower volume and capacity ratio; The tap density of powder is greater than 1.5g/cm
3The time, adopt native graphite to be difficult to processing, increased the preparation cost of material.
Composite carbon negative electrode material of lithium ion power battery of the present invention has graphite crystal interlamellar spacing d
002At 0.335nm～0.340nm, adopt the wide angle diffraction approach of powder X-ray RD to measure.During greater than 0.340nm, degree of graphitization reduces, and has reduced the charge/discharge capacity of negative material in the interlamellar spacing of graphite crystal.
The crystalline size Lc that composite carbon negative electrode material of lithium ion power battery composite graphite particles of the present invention has on the c of graphite crystal direction of principal axis is 50～150nm, at the crystalline size La of crystal basal plane orientation is 50～100nm, the graphite microcrystal size is the length that records at the c direction of principal axis, if crystallite size is less than 50nm, the lattice structure defects odds of graphite crystal increases, and to improving lithium ion embedding capacity therein adverse influence is arranged.Crystallite size La has influenced the diffusion velocity of lithium ion in graphite crystal again greater than 100nm, and then is unfavorable for the high current charge-discharge of battery.Lc and La measure by the wide angle diffraction approach of powder X-ray ray.
Composite carbon negative electrode material of lithium ion power battery of the present invention has average particulate diameter 5～60 μ m, adopts Britain Malvem Mastersizer 2000 laser particle size analyzers to measure.The average particulate diameter of graphite powder is the value at 50% accumulative total place of the volume cumulative distribution curve by the particle diameter that laser diffraction/the scattering method records.If average particulate diameter is less than 5 μ m, then the specific area of graphite powder increases, and makes thus to discharge and recharge the coulombic efficiency reduction.Greater than 60 μ m, lithium ion diffusion therein may need the long period, has influenced discharge performance, particularly high-rate performance or low temperature performance thus for average particulate diameter.The average particulate diameter of composite stone ink powder of the present invention thus is better at 5～60 μ m.And graphite powder preferably do not contain the coarse granule greater than 75 μ m that big electric current or low temperature performance is had adverse effect, do not contain the fine particle less than 5 μ m that is unfavorable for improving initial charge/discharge efficient yet.In addition, if contain when packing battery case into after coarse grained graphite powder is reeled as negative material making negative plate, concentrated stress is easy to be applied on the coarse granule, may puncture barrier film causes and produces internal short-circuit between the both positive and negative polarity, for broad particle distribution erose graphite powder, this problem more may take place.If the average particulate diameter of graphite powder is greater than 60 μ m, the possibility that comprises irregularly shaped particles so can increase.
The described composite graphite of being made up of spherical graphite matrix and surface coating layer thereof is as lithium ion battery negative material, be not easy to cause graphite crystal the c axle be parallel to aligning of collector direction, lithium ion enters and the resistance of deviating from graphite layers reduces, and has therefore improved the fast charging and discharging performance and the cycle performance of lithium ion battery.
The method of one or more graphite powders and binding agent mixing granulation is not limited especially, any known mixing granulator equipment all can use, preferred technology is to carry out below the softening point of said binding agent, such as, when used binding agent is pitch and tar, the temperature of mixing granulation is chosen in 70～300 ℃ carries out, and when said binding agent used resin, the temperature of mixing granulation was chosen in 20～100 ℃ and carries out
Subsequently, above-mentioned compound is carried out carbonization or graphitization processing, if used raw-material carbon content less than 99%, the binding agent addition is higher, at this moment impurity content is higher in the material, for guaranteeing to obtain better electrochemical performance, graphitization processing is essential, compound is pressed into required shape before carbonization or graphitization processing, briquetting process is not particularly limited, the pressure processing method of any making graphite electrode all can use, such as compression molding, and vibration moulding etc.Its density is 1.6～1.75g/cm after the moulding
3If density is less than 1.6g/m after the moulding
3, then the intensity of mold pressing aftershaping body is relatively poor, influences normally the carrying out of graphitizing process in later stage; If density is greater than 1.75g/cm after the moulding
3, then having increased the difficulty of moulding, the crushing process in later stage is difficult to carry out.Above-mentioned die forming process is not essential, in used raw-material carbon content greater than 99%, and used binding agent more after a little while, at this moment the content of impurity element is less, if carbon content and chemical property for material do not have higher requirement, can be without graphitization processing, then can be without compression molding, at this moment only need to pulverize said compound, adjust granularity to the value that needs.Described carbonization or graphitization are carried out in nonoxidizing atmosphere, for example, carry out in nitrogen, argon gas, vacuum or reducing atmosphere.Described carbonization is carried out for 450 ℃～1300 ℃ in temperature, and described graphitization temperature is 2200 ℃～3000 ℃.If graphitization temperature is lower than 2200 ℃, then graphite crystal can not be grown fully, and the non-carbon class of part impurity still is retained in the graphite, can influence charge/discharge capacity like this; If graphitization temperature is too high, then manufacturing cost increases, and also causes the distillation of graphite easily and influences yield.
The preparation method of composite carbon negative electrode material of lithium ion power battery of the present invention must handle through low-temperature carbonization, otherwise contain too much impurity element in the material during without graphitization processing, can't form the charge-discharge performance of satisfying the demand.
In comminution process subsequently, obtain the negative material of reasonable particle size distribution, described pulverization process is not particularly limited, and can use milling equipment commonly used such as high pressure flour mill, bar type mechanical crusher, low velocity impact formula nodularization pulverizer, air-flow vortex formula pulverizer, micronizer, ultra micro ball mill, internal classification impact type micro mist pulverizer or pendulum type ring roll pulverizer.
Embodiment 1, with spherical natural graphite powder 100 weight portions of average grain diameter 8 μ m, phosphorus content 95%, adds additive conductive black 2 weight portions, organic binder bond thermosetting phenolic resin 10 weight portions, and the solvent absolute ethyl alcohol mixes in right amount, solvent evaporated.Density 1.65g/cm behind the die mould
3, with compound graphitization 4 hours under 2800 ℃ of temperature, reduce to room temperature then, use the high pressure flour mill to pulverize the back and obtain average grain diameter 20 μ m composite carbon particles.As shown in Figure 2, find out by stereoscan photograph, the composite carbon particle is that spherical graphite and surface coated material with carbon element are formed, adopt NEC JEOLJSM-6380LV ESEM, the draw ratio that U.S. Millitrac particle image analyzer records this complex carbon material is 1.6, adopts the wide angle of powder X-ray ray diffraction approach to obtain the d of graphite crystal
002Be 0.3358nm, crystal average-size La=80nm, Lc=100nm adopts the test of BET method, and specific area is 2.8m
2/ g, the tap density that adopts QuantachromeAutoTap tap density instrument to record powder is 1.1/cm
3
Estimate the preparation of battery, adopt following method to prepare the 053048A rectangular lithium ion battery, adopt the composite carbon negative electrode material of lithium ion power battery of embodiment 1 step preparation, with binding agent butadiene-styrene rubber breast SBR, suspending agent carboxyl methyl cellulose, conductive black Super-P according to 95: 2.5: 1.5: 1 weight ratio is mixed, adding an amount of pure water sizes mixing as dispersant, evenly be coated on the Copper Foil, make negative plate through vacuumize, roll-in; Use LiCoO
2Be positive electrode active materials, mix according to 94: 3: 3 weight ratio with binding agent polyvinylidene fluoride PVDF, conductive agent Super-P, add an amount of N-methyl pyrrolidone NMP, be coated on the aluminium foil as dispersant furnishing slurry, and, be prepared into positive plate through vacuumize, roll-in; Use 1mol/L LiPF
6Three component mixed solvent EC: DMC: EMC=1: 1: 1, v/v solution was electrolyte, and microporous polypropylene membrane is a barrier film, is assembled into battery.The cycle performance test uses the electric current of 300mA to carry out the constant current charge-discharge experiment, and charging/discharging voltage is limited in 4.2～3.0 volts; 500mA is used in the fast charging and discharging test respectively, 750mA, and the electric current of 900mA carries out.Test result sees Table 1.
Embodiment 2, natural graphite powder 50 weight portions of average grain diameter 10 μ m, phosphorus content 99.9% and graphous graphite powder 50 weight portions of same particle sizes and carbon content are mixed, add binder pitch 10 weight portions, additive VGCF 1.5 weight portions mix coating under 150 ℃ of temperature, with compound carbonization treatment 4 hours under 1000 ℃ of temperature, reduce to room temperature then, adopt low velocity impact formula nodularization pulverizer to pulverize the back and obtain average grain diameter 20 μ m composite carbon particles.Stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is made up of the material with carbon element coating layer on spherical graphite and surface thereof, the draw ratio that is obtained this complex carbon material by the image analyzer analytical test is 3.6, adopts the wide angle of powder X-ray ray diffraction approach to obtain the d of graphite crystal
002Be 0.3365nm, crystal average-size La=50nm, Lc=150nm adopts the test of BET method, and specific area is 3.6m
2/ g.The tap density that adopts Quantachrome AutoTap tap density instrument to record powder is 1.08g/cm
3
Adopt the method identical to prepare battery, carry out electrochemical property test, the results are shown in Table 1 with embodiment 1.
Comparative Examples 1 is crushed to average grain diameter 20 μ m with Delanium, obtains the graphite granule of laminated structure, and draw ratio is 6, specific area 10m
2/ g, crystal layer spacing d
002Be 0.3358nm, crystalline size Lc is 50nm.
Adopt the method identical to prepare battery, carry out electrochemical property test, the results are shown in Table 1 with embodiment 1.
By the test result of table 1 as can be seen, compare with Comparative Examples 1, embodiment 1 and embodiment 2 have obtained better cycle performance and heavy-current discharge performance, after 500 circulations, embodiment 1 and embodiment 2 have obtained 88% and 90% capability retention respectively, and the capability retention of Comparative Examples 1 has been reduced to 70%, compare heavy-current discharge performance, when 900mA discharges and recharges, embodiment 1 and embodiment 2 have obtained the discharge capacity of 743mAh and 762mAh respectively, kept 94.1% and 94.6% of 300mAh discharge capacity, and Comparative Examples 1 only obtains the discharge capacity of 450mAh, is 71% of 300mA discharge capacity.
Embodiment 3, natural graphite powder 20 weight portions of average grain diameter 17 μ m, phosphorus content 99.9% and graphous graphite powder 80 weight portions of same particle sizes and carbon content are mixed, add coal tar pitch 20 weight portions, additive carbon nano-tube 1 weight portion mixes coating under 100 ℃ of temperature, carbonization treatment is 5 hours under 1100 ℃ of temperature, reduce to room temperature then, adopt air-flow vortex formula pulverizer to pulverize the back and obtain average grain diameter 18 μ m composite carbon particles.Stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is made up of the material with carbon element coating layer on spherical graphite and surface thereof, the draw ratio that is obtained this complex carbon material by the image analyzer analytical test is 2.6, adopts the wide angle of powder X-ray ray diffraction approach to obtain the d of graphite crystal
002Be 0.3368nm, crystalline size La=80nm, Lc=120nm adopts the test of BET method, and specific area is 2.6m
2/ g, the tap density that adopts QuantachromeAutoTap tap density instrument to record powder is 1.18g/cm
3
The composite carbon negative electrode material of lithium ion power battery of gained prepares electrode as follows: take by weighing 96 gram composite graphites, 2.5 gram SBR, 1.5 gram CMC, add an amount of pure water dispersant evenly after, be coated on the Copper Foil, make electrode through vacuumize, roll-in, with lithium is to electrode, 1MLiPF
6Three component mixed solvent EC: DMC: EMC=1: 1: 1, v/v solution was electrolyte, and microporous polypropylene membrane is a barrier film, is assembled into simulated battery, with 0.5mA/cm
2Current density (0.2C) is carried out the constant current charge-discharge experiment, charging/discharging voltage is limited in 0.005～2.0 volt, initial charge specific capacity, first discharge specific capacity and the irreversible capacity of test compound graphite, and at the specific discharge capacity of the 50th circulation, 0.5mA/cm is adopted in the fast charging and discharging performance evaluation
2Constant current charge, then respectively with 2.0mA/cm
2(0.8C), 4.0mA/cm
2(1.6C), 5.0mA/cm
2Discharging current discharge (2.0C), the variation of electric discharge capacity.Test result is listed in table 2.
Embodiment 4, natural graphite powder 60 weight portions and average grain diameter 10 μ m, phosphorus content 99% graphous graphite powder 40 weight portions of average grain diameter 6 μ m, phosphorus content 96% are mixed, add coal tar pitch 15 weight portions, coal tar 10 weight portions, additive conductive black Super-P 2 weight portions mix coating, density 1.7g/m behind the die mould under 100 ℃ of temperature
3, through 800 ℃ of carbonizations 2 hours, graphitization was 10 hours under 3000 ℃ of temperature, reduces to room temperature then under argon shield, adopted the ultra micro ball mill to pulverize the back and obtained average grain diameter 15 μ m composite carbon particles.Stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is made up of the material with carbon element coating layer on spherical graphite and surface thereof, the draw ratio that is obtained this complex carbon material by the image analyzer analytical test is 3.0, adopts the wide angle of powder X-ray ray diffraction approach to obtain the d of graphite crystal
002Be 0.3360nm, average crystalline size La=60nm, Lc=100nm adopts the test of BET method, and specific area is 3.6m
2/ g, the tap density that adopts Quantachrome AutoTap tap density instrument to record powder is 1.0g/cm
3
Adopt the method identical to prepare battery, carry out electrochemical property test, the results are shown in Table 2 with embodiment 3.
Embodiment 5; natural graphite powder 20 weight portions and average grain diameter 11 μ m, phosphorus content 99.9% graphous graphite powder 80 weight portions of average grain diameter 20 μ m, phosphorus content 99.9% are mixed; add thermosetting phenolic resin 1 weight portion; additive acetylene black 1.5 weight portions mix coating under 30 ℃ of temperature; afterwards compound after 10 hours, is being reduced to room temperature through 800 ℃ of carbonizations under the nitrogen protection.Adopt internal classification impact type micro mist pulverizer to pulverize the back and obtain average grain diameter 22 μ m composite carbon particles.Stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is made up of the material with carbon element coating layer on spherical graphite and surface thereof, the draw ratio that is obtained this complex carbon material by the image analyzer analytical test is 4.0, adopts the wide angle of powder X-ray ray diffraction approach to obtain the d of graphite crystal
002Be 0.3378nm, average crystalline size La=50nm, Lc=100nm adopts the test of BET method, and specific area is 4.0m
2/ g, the tap density that adopts Quantachrome AutoTap tap density instrument to record powder is 0.97g/cm
3
Adopt the method identical to prepare battery, carry out electrochemical property test, the results are shown in Table 2 with embodiment 3.
Embodiment 6, natural graphite powder 20 weight portions of average grain diameter 0.1 μ m, phosphorus content 99.9% and graphous graphite powder 80 weight portions of same particle sizes and carbon content are mixed, add coal tar pitch 50 weight portions, additive carbon nano-tube 5 weight portions mix coating, density 1.65g/cm behind the die mould under 100 ℃ of temperature
3, carbonization treatment is 5 hours under 1300 ℃ of temperature, reduces to room temperature then, with goods graphitization 4 hours under 2200 ℃ of temperature, reduces to room temperature then, adopts air-flow vortex formula pulverizer to pulverize the back and obtains average grain diameter 18 μ m composite carbon particles.Stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is made up of the material with carbon element coating layer on spherical graphite and surface thereof, the draw ratio that is obtained this complex carbon material by the image analyzer analytical test is 2.4, adopts the wide angle of powder X-ray ray diffraction approach to obtain the d of graphite crystal
002Be 0.3368nm, crystalline size La=80nm, Lc=120nm adopts the test of BET method, and specific area is 3.6m
2/ g, the tap density that adopts Quantachrome AutoTap tap density instrument to record powder is 1.08g/cm
3
Adopt the method identical to prepare battery, carry out electrochemical property test, the results are shown in Table 2 with embodiment 3.
Embodiment 7; natural graphite powder 20 weight portions and average grain diameter 11 μ m, phosphorus content 99.9% graphous graphite powder 80 weight portions of average grain diameter 40 μ m, phosphorus content 99.9% are mixed; add thermosetting phenolic resin 1 weight portion; additive acetylene black 0.1 weight portion mixes coating under 30 ℃ of temperature; afterwards compound after 10 hours, is being reduced to room temperature through 450 ℃ of carbonizations under the nitrogen protection.Adopt internal classification impact type micro mist pulverizer to pulverize the back and obtain average grain diameter 22 μ m composite carbon particles.Stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is made up of the material with carbon element coating layer on spherical graphite and surface thereof, the draw ratio that is obtained this complex carbon material by the image analyzer analytical test is 3.5, adopts the wide angle of powder X-ray ray diffraction approach to obtain the d of graphite crystal
002Be 0.3378nm, average crystalline size La=50nm, Lc=100nm adopts the test of BET method, and specific area is 4.0m
2/ g, the tap density that adopts Quantachrome AutoTap tap density instrument to record powder is 0.98g/cm
3
Adopt the method identical to prepare battery, carry out electrochemical property test, the results are shown in Table 2 with embodiment 3.
Comparative Examples 2 is crushed to average grain diameter 20 μ m with native graphite, obtains the graphite granule of laminated structure, and average aspect ratio is 7, specific area 11m
2/ g, crystal layer spacing d
002Be 0.336nm, crystalline size Lc is 200nm.
Adopt the method identical to prepare battery, carry out electrochemical property test, the results are shown in Table 2 with embodiment 3.
Found out that by table 2 composite carbon negative electrode material of lithium ion power battery of the present invention has higher discharge capacity, irreversible capacity is lower first, and cycle performance and multiplying power discharging property excellence are specially adapted to the negative material that lithium-ion-power cell is used.In addition, because composite carbon negative electrode material of lithium ion power battery of the present invention can use cheap natural graphite powder and graphous graphite powder, preparation process is simple, and cost is low, therefore has great marketing and application prospect.
Table 1 electrochemical property test
Table 2 electrochemical property test
Claims (11)
1. composite carbon negative electrode material of lithium ion power battery, it is characterized in that: described composite carbon negative electrode material of lithium ion power battery is the composite graphite particles by binding agent combination or combination, spherical in shape or class is spherical, the composite graphite particles surface is dispersed with additive; The weight ratio that composite graphite particles comprises is: natural graphite powder, graphous graphite powder or natural graphite powder mix with graphous graphite powder, account for the additive of graphite powder weight 0.1～5%, account for the binding agent of graphite powder weight 1～50%.
2. according to claims 1 described composite carbon negative electrode material of lithium ion power battery, it is characterized in that: the average grain diameter of described composite graphite particles is 5～60 μ m, draw ratio between 1.5～4, specific area 1.0～4.0m
2/ g, tap density 0.7～1.5g/cm
3, crystal layer spacing d
002Between 0.335～0.340nm.
3. according to claims 1 described composite carbon negative electrode material of lithium ion power battery, it is characterized in that: the crystalline size that described composite graphite particles has on the c of graphite crystal direction of principal axis is 50～150nm, is 50～100nm at the crystalline size of crystal basal plane orientation.
4. according to claims 1 described composite carbon negative electrode material of lithium ion power battery, it is characterized in that: described additive is conductive black, acetylene black, gas-phase growth of carbon fibre, carbon nano-tube or nano-sized carbon microballoon.
5. according to claims 1 described composite carbon negative electrode material of lithium ion power battery, it is characterized in that: described binding agent be pitch, tar or resin any, two or three mixing.
6. the preparation method of a composite carbon negative electrode material of lithium ion power battery may further comprise the steps:
One, with granularity be 0.1 μ m to 40 μ m, fixed carbon content 〉=94% graphite powder, account for graphite powder weight 0.1～5% additive, account for the binding agent of graphite powder weight 1～50%, mixing granulation; Two, with mixed pellet extrusion modling, its density is 1.6～1.75g/cm after the moulding
3, roasting afterwards, dipping; Three, molding mass is carried out graphitization processing or carbonization and graphitization processing, heating is 450 ℃ to 3000 ℃ in protective gas, is incubated 1 to 10 hour, reduces to room temperature then; Four, above-mentioned complex carbon material is pulverized, average grain diameter is 5～60 μ m.
7. the preparation method of composite carbon negative electrode material of lithium ion power battery according to claim 6 is characterized in that: described graphite powder is one or more mixing in natural flake graphite, micro crystal graphite or the Delanium.
8. the preparation method of composite carbon negative electrode material of lithium ion power battery according to claim 6, it is characterized in that: described additive is conductive black, acetylene black, gas-phase growth of carbon fibre VGCF, carbon nano-tube or nano-sized carbon microballoon.
9. the preparation method of composite carbon negative electrode material of lithium ion power battery according to claim 6, it is characterized in that: described binding agent is a kind of or above-mentioned two or three mixture in pitch, tar or the resin.
10. the preparation method of composite carbon negative electrode material of lithium ion power battery according to claim 6, it is characterized in that: when described binding agent is pitch and tar, the temperature of mixing granulation is chosen in 70～300 ℃ and carries out, when binding agent used resin, the temperature of mixing granulation was chosen in 20～100 ℃ and carries out.
11. the preparation method of a composite carbon negative electrode material of lithium ion power battery may further comprise the steps:
One, with granularity be 0.1 μ m to 40 μ m, fixed carbon content 〉=94% graphite powder, account for graphite powder weight 0.1～5% additive, account for the binding agent of graphite powder weight 1～50%, mixing granulation; Two, mixed pellet is carried out low-temperature carbonization and handle, heating is 450 ℃ to 1300 ℃ in protective gas, is incubated 1 to 10 hour, reduces to room temperature then; Three, above-mentioned complex carbon material is pulverized, average grain diameter is 5～60 μ m.
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