CN100585921C - Lithium-ion cell composite carbon cathode material and preparing method - Google Patents
Lithium-ion cell composite carbon cathode material and preparing method Download PDFInfo
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- CN100585921C CN100585921C CN200610060814A CN200610060814A CN100585921C CN 100585921 C CN100585921 C CN 100585921C CN 200610060814 A CN200610060814 A CN 200610060814A CN 200610060814 A CN200610060814 A CN 200610060814A CN 100585921 C CN100585921 C CN 100585921C
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Abstract
This invention discloses a complex carbon negative material of Li ionic batteries and its preparation method, in which, the material is natural graphite micro-powder, artificial graphite micro-powder or complex graphite particles of natural and artificial graphite micro-powder combined by binding agents, the hexagon carbon layers of graphite crystals are arrayed randomly, the particles include nm or sub-mum holes, the preparation method includes: mixed-prilling, extruding to molding, carbonized process or graphitized process, heating and cooling and crushing.
Description
Technical field
The present invention relates to a kind of cell negative electrode material and preparation method thereof, particularly a kind of lithium ion battery composite carbon cathode material and its preparation method.
Background technology
The oil crisis in the 60 to 70's of last century and the continuous increase of population become increasingly conspicuous the contradiction of shortage of resources, and particularly in today that people more and more pay attention to environmental protection, green power supply has obtained develop rapidly.Lithium ion battery has been exactly the secondary cell of new generation after Ni-MH battery since the eighties of last century the nineties.And because of its have operating voltage height, energy density big, have extended cycle life, advantages such as self discharge is little, memory-less effect, become the chemical power source of present high-grade consumer electronics first-selection, and be penetrated into sophisticated technology fields such as Aero-Space, military affairs.Be accompanied by the demand that it grows with each passing day, lithium ion battery is just becoming the emphasis and the focus of new century scientific and technical research and exploitation.
The negative material of commercialization lithium ion battery is material with carbon element at present, wherein graphite type material comprises native graphite, the Delanium by coke, pitch and the preparation of various organic substance graphitization etc., is used widely because of it has high charge/discharge capacity, favorable charge-discharge platform, wide material sources, cost is low.But, in the Delanium of complete native graphite of graphite crystal growth and the graphitization preparation by coke etc., interlayer adhesion on the c of crystal direction of principal axis is lower than the adhesion on the crystal basal plane orientation, therefore be easy to form sheet-like particle in the crushing process when powder preparing 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.In addition, 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 microparticles 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 lithium ion battery composite carbon cathode material and its preparation method, the technical problem that solves is to make cathode material of composite carbon in use for lithium ion battery have less irreversible capacity loss first, has fast charging and discharging performance and good cycle performance.
The present invention is by the following technical solutions: a kind of cathode material of composite carbon in use for lithium ion battery, described cathode material of composite carbon in use for lithium ion battery be native graphite micro mist, Delanium micro mist or native graphite micro mist with the Delanium micro mist by binding agent combination or the composite graphite particles that combines, the hexagonal carbon-coating random alignment of graphite crystal, granule interior includes nanometer or sub-micron hole.
Composite graphite particles of the present invention is to pass through the binding agent be combined into by 3 to 2175 graphite particulates, has the spheroidal microscopic feature of sphere or class.
The micropore quantity that composite graphite particles of the present invention inside is contained, size is 0.5～2.2cm at the pore volume of 10nm～10 μ m
3/ g.
The crystalline size that composite graphite negative electrode material 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.
The average grain diameter of composite graphite negative electrode material of the present invention is 5～60 μ m, draw ratio between 1.5～4.0, specific area 1.0～6.0m
2/ g, tap density 0.7～1.5g/cm
3, crystal layer spacing d
002Between 0.335～0.338nm.
Binding agent of the present invention be pitch, tar and resin any, two or three mixing.
A kind of preparation method of cathode material of composite carbon in use for lithium ion battery, may further comprise the steps: one, be the graphite microparticles of 0.3～30 μ m, fixed carbon content 〉=90.0% granularity, the binding agent of graphite microparticles weight 1～40%, mixing granulation adds the graphitization catalyst of graphite microparticles and weight of binder 0.01～10% simultaneously; Two, with mixed pellet extrusion modling, its density is 1.3～1.9g/cm after the moulding
3Three, 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 graphite microparticles that method of the present invention adopts be in natural flake graphite, micro crystal graphite and the Delanium any, two or three mixing.
The binding agent that method of the present invention adopts be in pitch, tar and the resin any, two or three mixing.
When the binding agent that method of the present invention adopts 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.
The graphitization catalyst that method of the present invention adopts is simple substance or its compound of boron, silicon, beryllium, aluminium, titanium, nickel, cobalt element, and the average grain diameter of graphitization catalyst is below 60 μ m.
The extrusion modling device therefor that method of the present invention adopts is: mix and pinch pot, press; The pulverizer of pulverizing usefulness is airslide disintegrating mill, high pressure flour mill, bar type mechanical crusher, low velocity impact formula nodularization pulverizing, air-flow vortex pulverizing mill, micronizer, ultra micro ball mill, internal classification impact type micro mist pulverizer or pendulum type ring roll pulverizer.
A kind of preparation method of cathode material of composite carbon in use for lithium ion battery may further comprise the steps: one, be the graphite microparticles of 0.3 to 30 μ m, fixed carbon content 〉=90.0% with granularity, and the binding agent of graphite microparticles weight 1～40%, mixing granulation; Two, mixed pellet is carried out low-temperature carbonization and handle, heating is 450 ℃ to 3000 ℃ in protective gas, is incubated 1 to 10 hour, reduces to room temperature then; Three, above-mentioned complex carbon material is pulverized.
The present invention compared with prior art, adopt the native graphite micro mist, the ion secondary battery cathode material lithium that Delanium micro mist or native graphite micro mist and Delanium micro mist make by binding agent combination or the composite graphite particles that combines, the hexagonal carbon-coating random alignment of graphite crystal, granule interior includes nanometer or sub-micron hole, 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 all kinds of portable device, electric tool, the electric vehicle lithium ion battery negative material.
Description of drawings
Fig. 1 is the preceding electromicroscopic photograph of graphite microparticles heat treatment of the embodiment of the invention 1.
Fig. 2 is the electromicroscopic photograph of the cathode material of composite carbon in use for lithium ion battery of the embodiment of the invention 1.
Fig. 3 be the embodiment of the invention 1 graphite microparticles heat treatment before XRD figure.
Fig. 4 is the XRD figure of the cathode material of composite carbon in use for lithium ion 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 cathode material of composite carbon in use for lithium ion battery of the present invention is made up of by binding agent native graphite micro mist, Delanium micro mist or native graphite micro mist and Delanium micro mist, composite graphite particles is by binding agent combination or be combined into by 3 to 2175 graphite particulates, has the spheroidal microscopic feature of sphere or class, the hexagonal carbon-coating random alignment of graphite crystal, granule interior includes 0.5～2.2cm
3The nanometer of/g or sub-micron hole, adopt methods such as scanning electron microscopy, particle pore-size distribution analyzer, the wide angle of powder X-ray RD diffraction, the micropore quantity that the granule interior of mensuration complex carbon material contains, size is 0.5～2.2cm at the pore cumulative volume of 10nm～10 μ m
3/ g, 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; The average grain diameter of cathode material of composite carbon in use for lithium ion battery is 5～60 μ m, draw ratio between 1.5～4, specific area 1.0～6.0m
2/ g, tap density 0.7～1.5g/cm
3, crystal layer spacing d
002Between 0.335～0.338nm.Binding agent adopt pitch, tar and resin any, two or three mixing.
The preparation method of cathode material of composite carbon in use for lithium ion battery of the present invention, may further comprise the steps: one, be 0.3 to 30 μ m granularity, the graphite microparticles of fixed carbon content 〉=90.0%, and the binding agent of graphite microparticles weight 1～40%, mixing granulation adds the graphitization catalyst of graphite microparticles and weight of binder 0.01～10% simultaneously; Two, with mixed pellet extrusion modling, its density is 1.3～1.9g/cm after the moulding
3Three, molding mass is carried out carbonization treatment or graphitization processing, heating is 450 ℃ to 3000 ℃ in protective gas, is incubated 1 to 10 hour, drops to room temperature at protective atmosphere then; Four, above-mentioned complex carbon material is pulverized; Three, above-mentioned complex carbon material is pulverized; Five, carry out purification process.
The preparation method's of cathode material of composite carbon in use for lithium ion battery of the present invention graphite microparticles be in natural flake graphite, micro crystal graphite and the Delanium any, two or three mixing; The cooperation ratio of graphite microparticles is the native graphite micro mist: Delanium micro mist=0～100: 100～0.That is be to use native graphite micro mist or Delanium micro mist, perhaps the two mixes in certain proportion.The particle diameter of used micro mist is less than the particle diameter of prepared complex carbon material.
Binding agent be in pitch, tar and the resin any, two or three mixing; Graphitization catalyst is simple substance or its compound of boron, silicon, beryllium, aluminium, titanium, nickel, cobalt element;
Protective gas is nitrogen, argon gas, vacuum or reducing gas, and tunnel cave well-known to those skilled in the art or graphitizing furnace are adopted in heat treatment, and purifying adopts sour method of purification, oxidizing process and network and method purification process technology.
As shown in Figure 1, it is irregularly shaped to be bulk, flakey etc. before graphite microparticles of the present invention is handled; Spherical in shape or class is spherical after bonding granulation and heat treatment, as shown in Figure 2, 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 microparticles of the present invention about the angle of diffraction 43.3 degree and 46.0 degree before graphitization processing, be six sides phase and rhombus mixture mutually; Rhombus phase diffraction maximum disappears after the comparison diagram 4, cathode material of composite carbon in use for lithium ion battery heat treatment, and the rhombus inversion of phases is six more stable side's phases.
As shown in Figure 2, cathode material of composite carbon in use for lithium ion 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.Above-mentioned 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 irregular shapes such as flakey, laminar, 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 intermediate mediums such as binding agents between the graphite particulate; " combination " is meant the state that flocks together owing to factors such as shape, molecular separating force and surface tension 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 size of single graphite granule is below 2/3 of second particle size that single graphite granule is formed at 0.3～30 μ m, and 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 Malvern Mastersizer 2000 laser particle size analyzers to measure.
The draw ratio that cathode material of composite carbon in use for lithium ion battery particle of the present invention has is between 1.5～4.Draw ratio adopts following method definition, by the graphite granule of microscopically amplification, if the major axis dimension of individual particle is a, minor axis dimension is b, then draw ratio is a/b, and the present invention adopts NEC JEOL JSM-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.
Cathode material of composite carbon in use for lithium ion battery of the present invention also has 1.0～6.0m
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 6.0m
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.
Cathode material of composite carbon in use for lithium ion battery of the present invention has graphite crystal interlamellar spacing d
002At 0.335nm～0.338nm, adopt the wide angle diffraction approach of powder X-ray RD to measure.During greater than 0.338nm, 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 cathode material of composite carbon in use for lithium ion battery 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.
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 within the scope of the present invention.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.
Cathode material of composite carbon in use for lithium ion battery of the present invention has average particulate diameter 5～60 μ m, adopts Britain Malvern Mastersizer 2000 laser particle size analyzers to measure.
Cathode material of composite carbon in use for lithium ion battery granule interior of the present invention also has the micropore of some, is benchmark with the weight of graphite granule, and size is 0.5～2.2cm at the pore volume of 10nm～10 μ m
3/ g uses U.S. Quantachrome Poremaster 60 mercury apertometers to measure.Adopt such graphite granule as negative material, therefore the absorption that micropore relaxes that volumetric expansion that causes in the repeated charge process and contraction are contained by inside has suppressed the structural deterioration of electrode, has improved cycle performance.At described pore volume less than 0.5cm
3/ g, the cycle performance of material worsens; At described pore volume greater than 2.2cm
3/ g has reduced the volume and capacity ratio of material.
The above-mentioned temper carbon particle of being made up of a plurality of graphite particulates 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.
As graphitization catalyst, can use simple substance or its compound of elements such as boron, silicon, beryllium, aluminium, titanium, nickel, cobalt, the average grain diameter of graphitization catalyst is below 60 μ m, when the particle diameter of catalyst is excessive, graphitization growth can not evenly be carried out, and influences the giving full play to of discharge capacity of negative material manufactured goods.If the addition of catalyst is less than 0.01%, with the percetage by weight metering of catalyst elements, growing up of graphite crystal is restricted, and the porosity of manufactured goods is too small, influences the discharge capacity and the cycle performance of battery; If the addition of catalyst is greater than 10%, with the percetage by weight metering of catalyst elements, the porosity of then drawing abillity variation, and manufactured goods is excessive, influences the volume and capacity ratio of material.The effect of catalyst is to reduce the required energy of graphitizing process, quickens the graphitization process, and catalyst forms little pore by discharging in the graphite granule in graphitizing process simultaneously, thereby gives negative material preferable performance of the present invention.In these graphitization catalyst, the carbide of boron and silicon and oxide are more excellent selections.
The method of one or more graphite microparticles 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, in case of necessity, before carbonization or graphitization processing, compound is pressed into required shape, 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 1.3～1.9g/cm after the moulding
3If density is less than 1.3g/cm 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 1.9g/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, if at this moment material without graphitization processing, then can only need to pulverize said compound without compression molding, adjusts granularity to the value that needs.Said carbonization or graphitization are carried out in nonoxidizing atmosphere, for example, carry out in nitrogen, argon gas, vacuum or reducing atmosphere.Said carburizing temperature is carried out at 450 ℃～1500 ℃, and said graphitization temperature is 2200 ℃～3000 ℃.If graphitization temperature is lower than 2200 ℃, then graphite crystal can not be grown fully, and the part graphitization catalyst 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 can cause the distillation of graphite and influences yield.
Composite carbon negative polar material of the present invention also can be handled but must pass through low-temperature carbonization without graphitization processing.When handling, need not add graphitization catalyst in the aforesaid mixing granulation stage without high temperature graphitization.
In comminution process subsequently, obtain the negative material of reasonable particle size distribution, said 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, native graphite micro mist 100 weight portions with average grain diameter 5 μ m, phosphorus content 93.6%, add petroleum asphalt 20 weight portions, coal tar 10 weight portions, carborundum 10 (addition of amounting to Si is 5.3wt%) weight portion mixing granulation under 150 ℃ of temperature, be pressed into cylindrical graphite block, die mould density 1.9g/cm
3, graphitization is 4 hours under 2800 ℃ of temperature, reduces to room temperature then, uses the high pressure flour mill to pulverize the back and obtains average grain diameter 20 μ m composite carbon particles.As shown in Figure 2, stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is the second particle by a plurality of graphite microparticles be combined intos, by 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 0.3356nm, crystal average-size La=80nm, Lc=100nm adopts the test of BET method, and specific area is 2.6m
2/ g, the tap density that adopts Quantachrome AutoTap tap density instrument to record powder is 1.02g/cm
3, use Quantachrome PoreMaster 60 mercury injection apparatuses to measure powder interior pore volume and pore-size distribution, size is 0.8cm at the pore volume of 10nm～10 μ m
3/ g.
Estimate the preparation of battery, adopt following method to prepare the 053048A rectangular lithium ion battery, adopt the cathode material of composite carbon in use for lithium ion 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/LLiPF
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, native graphite micro mist 50 weight portions of average grain diameter 10 μ m, phosphorus content 96.4% and Delanium micro mist 50 weight portions of same particle sizes and carbon content are mixed, add petroleum asphalt 10 weight portions, coal tar 20 weight portions, boron carbide 17 weight portions (addition of amounting to B is 10wt%) mixing granulation under 150 ℃ of temperature, be pressed into cylindrical graphite block, die mould density 1.65g/cm
3Graphitization is 1 hour under 3000 ℃ of temperature, reduces to room temperature then, adopts low velocity impact formula nodularization pulverizer to pulverize the back and obtains average grain diameter 20 μ m composite carbon particles.Stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is the second particle by a plurality of graphite microparticles be combined intos, 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 0.3368nm, crystal average-size La=50nm, Lc=150nm adopts the test of BET method, and specific area is 4.6m
2/ g.The tap density that adopts Quantachrome AutoTap tap density instrument to record powder is 0.98g/cm
3, use Quantachrome PoreMaster 60 mercury injection apparatuses to measure powder interior pore volume and pore-size distribution, size is 1.1cm at the pore volume of 10nm～10 μ m
3/ g.
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 90% and 89% capability retention respectively, and the capability retention of Comparative Examples 1 has been reduced to 70%, the contrast heavy-current discharge performance, when 900mA discharges and recharges, embodiment 1 and embodiment 2 have obtained the discharge capacity of 690mAh and 620mAh respectively, kept 85% and 79% of 300mAh discharge capacity, and Comparative Examples 1 only obtains the discharge capacity of 450mAh, is 71% of 300mA discharge capacity.
Embodiment 3, native graphite micro mist 20 weight portions of average grain diameter 10 μ m, phosphorus content 93.8% and Delanium micro mist 80 weight portions of same particle sizes and carbon content are mixed, add coal tar pitch 20 weight portions, coal tar 20 weight portions, carborundum 0.02 (addition of amounting to Si is 0.01wt%) weight portion mixing granulation under 100 ℃ of temperature, be pressed into cylindrical graphite block, die mould density 1.4g/cm
3Graphitization is 5 hours under 3000 ℃ 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 the second particle by a plurality of graphite microparticles be combined intos, 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 Quantachrome AutoTap tap density instrument to record powder is 0.99g/cm
3, use Quantachrome PoreMaster 60 mercury injection apparatuses to measure powder interior pore volume and pore-size distribution, size is 1.0cm at the pore volume of 10nm～10 μ m
3/ g.
The gained cathode material of composite carbon in use for lithium ion battery 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, native graphite micro mist 60 weight portions and average grain diameter 40 μ m, phosphorus content 99.9% Delanium micro mist 40 weight portions of average grain diameter 1 μ m, phosphorus content 92.6% are mixed, add coal tar pitch 15 weight portions, coal tar 10 weight portions, boron oxide 10 weight portions (addition of amounting to B is 2.48wt%) mixing granulation under 100 ℃ of temperature, be pressed into cylindrical module, die mould density 1.3g/cm
3, through 800 ℃ of carbonizations after 2 hours, graphitization is 10 hours under 3000 ℃ of temperature, reduces to room temperature then under argon shield, adopts the ultra micro ball mill to pulverize the back and obtains average grain diameter 15 μ m composite carbon particles.Stereoscan photograph by this composite carbon particle is found out, the composite carbon particle is the second particle by a plurality of graphite microparticles be combined intos, 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 QuantachromeAutoTap tap density instrument to record powder is 1.0g/cm
3, use Quantachrome PoreMaster 60 mercury injection apparatuses to measure powder interior pore volume and pore-size distribution, size is 0.8cm at the pore volume of 10nm～10 μ m
3/ g.
Adopt the method identical to prepare battery, carry out electrochemical property test, the results are shown in Table 2 with embodiment 3.
Embodiment 5; native graphite micro mist 20 weight portions and average grain diameter 1 μ m, phosphorus content 99.9% Delanium micro mist 80 weight portions of average grain diameter 40 μ m, phosphorus content 91.0% are mixed; add thermosetting phenolic resin 1 weight portion; mixing granulation under 30 ℃ of temperature; do not add graphitization catalyst; 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 the second particle by a plurality of graphite microparticles be combined intos, 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 0.7g/cm
3, use Quantachrome PoreMaster 60 mercury injection apparatuses to measure powder interior pore volume and pore-size distribution, size is 2.2cm at the pore volume of 10nm～10 μ m
3/ g.
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 cathode material of composite carbon in use for lithium ion 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 cathode material of composite carbon in use for lithium ion battery of the present invention can use cheap native graphite micro mist and Delanium micro mist, for producing the byproduct of other graphite products, raw material are inexpensive, the recycling of a large amount of byproduct that solves, and 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 (8)
1. cathode material of composite carbon in use for lithium ion battery, it is characterized in that: the described cathode material of composite carbon in use for lithium ion battery composite graphite particles that to be the native graphite micro mist combine by binding agent with the Delanium micro mist, the hexagonal carbon-coating random alignment of graphite crystal, granule interior includes nanometer or sub-micron hole;
Described composite graphite particles is to pass through the binding agent be combined into by 3 to 2175 graphite particulates, has the spheroidal microscopic feature of sphere or class;
The micropore quantity that described composite graphite particles inside is contained, size is 0.5～2.2cm at the pore volume of 10nm～10 μ m
3/ g;
The crystalline size that described composite carbon negative polar material 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;
The average grain diameter of described composite carbon negative polar material is 5～60 μ m, draw ratio between 1.5～4.0, specific area 1.0～6.0m
2/ g, tap density 0.7～1.5g/cm
3, crystal layer spacing d
002Between 0.335～0.338nm;
Described binding agent be pitch, tar and resin any, two or three mixing;
This composite carbon negative polar material is prepared by first kind of preparation method, may further comprise the steps:
One, with granularity be the graphite microparticles of 0.3-30 μ m, fixed carbon content 〉=90.0%, the binding agent of graphite microparticles weight 1～40%, mixing granulation adds the graphitization catalyst of graphite microparticles and weight of binder 0.01～10% simultaneously;
When described binding agent 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;
Two, with mixed pellet extrusion modling, its density is 1.3～1.9g/cm after the moulding
3
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, the complex carbon material of gained is pulverized;
Perhaps, this composite carbon negative polar material is prepared by second kind of preparation method, may further comprise the steps:
One, with granularity is the graphite microparticles of 0.3 to 30 μ m, fixed carbon content 〉=90.0%, the binding agent of graphite microparticles weight 1～40%, mixing granulation;
Two, mixed pellet is carried out low-temperature carbonization and handle, heating is 450 ℃ to 3000 ℃ in protective gas, is incubated 1 to 10 hour, reduces to room temperature then;
Three, the complex carbon material of gained is pulverized.
2. cathode material of composite carbon in use for lithium ion battery according to claim 1, described graphitization catalyst are simple substance or its compound of boron, silicon, beryllium, aluminium, titanium, nickel, cobalt element, and the average grain diameter of graphitization catalyst is below 60 μ m.
3. cathode material of composite carbon in use for lithium ion battery according to claim 1, described extrusion modling device therefor is pinched pot, press for mixing.
4. cathode material of composite carbon in use for lithium ion battery according to claim 1, the pulverizer of described pulverizing usefulness are airslide disintegrating mill, high pressure flour mill, bar type mechanical crusher, low velocity impact formula nodularization pulverizing, air-flow vortex pulverizing mill, micronizer, ultra micro ball mill, internal classification impact type micro mist pulverizer or pendulum type ring roll pulverizer.
5. cathode material of composite carbon in use for lithium ion battery according to claim 1, described cathode material of composite carbon in use for lithium ion battery is mixed by native graphite micro mist 50 weight portions of average grain diameter 10 μ m, phosphorus content 96.4% and Delanium micro mist 50 weight portions of same particle sizes and carbon content, add petroleum asphalt 10 weight portions, coal tar 20 weight portions, boron carbide 17 weight portions, mixing granulation under 150 ℃ of temperature is pressed into cylindrical graphite block, and die mould density is 1.65g/cm
3, graphitization is 1 hour under 3000 ℃ of temperature, reduces to room temperature then, and adopting low velocity impact formula nodularization pulverizer to pulverize back acquisition average grain diameter is the composite graphite particles of 20 μ m; The draw ratio of gained composite graphite particles is 3.6, the d of graphite crystal
002Be 0.3368nm, crystal average-size La=50nm, Lc=150nm, specific area is 4.6m
2/ g, the tap density of powder is 0.98g/cm
3, the powder inside dimension is 1.1cm at the pore volume of 10nm～10 μ m
3/ g.
6. cathode material of composite carbon in use for lithium ion battery according to claim 1, described cathode material of composite carbon in use for lithium ion battery is mixed by native graphite micro mist 20 weight portions of average grain diameter 10 μ m, phosphorus content 93.8% and Delanium micro mist 80 weight portions of same particle sizes and carbon content, add coal tar pitch 20 weight portions, coal tar 20 weight portions, carborundum 0.02 weight portion, mixing granulation under 100 ℃ of temperature is pressed into cylindrical graphite block, and die mould density is 1.4g/cm
3Graphitization is 5 hours under 3000 ℃ of temperature, reduces to room temperature then, adopts air-flow vortex formula pulverizer to pulverize the composite graphite particles that the back obtains average grain diameter 18 μ m; The draw ratio of gained composite graphite particles is 2.6, and the d002 of graphite crystal is 0.3368nm, crystalline size La=80nm, and Lc=120nm, specific area is 2.6m
2/ g, the tap density of powder is 0.99g/cm
3, the powder inside dimension is 1.0cm at the pore volume of 10nm～10 μ m
3/ g.
7. cathode material of composite carbon in use for lithium ion battery according to claim 1, described cathode material of composite carbon in use for lithium ion battery is mixed by native graphite micro mist 60 weight portions and average grain diameter 40 μ m, phosphorus content 99.9% Delanium micro mist 40 weight portions of average grain diameter 1 μ m, phosphorus content 92.6%, add coal tar pitch 15 weight portions, coal tar 10 weight portions, boron oxide 10 weight portions, mixing granulation under 100 ℃ of temperature is pressed into cylindrical module, and die mould density is 1.3g/cm
3, through 800 ℃ of carbonizations after 2 hours, graphitization is 10 hours under 3000 ℃ of temperature, reduces to room temperature then under argon shield, adopts the ultra micro ball mill to pulverize the composite graphite particles that the back obtains average grain diameter 15 μ m; The draw ratio of gained composite graphite particles is 3.0, the d of graphite crystal
002Be 0.3360nm, average crystalline size La=60nm, Lc=100nm, specific area is 3.6m
2/ g, the tap density of powder is 1.0g/cm
3, the powder inside dimension is 0.8cm at the pore volume of 10nm～10 μ m
3/ g.
8. cathode material of composite carbon in use for lithium ion battery according to claim 1, described cathode material of composite carbon in use for lithium ion battery is by average grain diameter 40 μ m, native graphite micro mist 20 weight portions of phosphorus content 91.0% and average grain diameter 1 μ m, phosphorus content 99.9% Delanium micro mist 80 weight portions mix, add thermosetting phenolic resin 1 weight portion, mixing granulation under 30 ℃ of temperature, do not add graphitization catalyst, afterwards with compound under the nitrogen protection through 800 ℃ of carbonizations after 10 hours, reduce to room temperature, adopt internal classification impact type micro mist pulverizer to pulverize the composite graphite particles that the back obtains average grain diameter 22 μ m; The draw ratio of gained composite graphite particles is 4.0, the d of graphite crystal
002Be 0.3378nm, average crystalline size La=50nm, Lc=100nm, specific area is 4.0m
2/ g, the tap density of powder is 0.7g/cm
3, the powder inside dimension is 2.2cm at the pore volume of 10nm～10 μ m
3/ g.
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