CN103000867A - Composite graphite negative electrode material with high energy density, and preparation method and application thereof - Google Patents
Composite graphite negative electrode material with high energy density, and preparation method and application thereof Download PDFInfo
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- CN103000867A CN103000867A CN201210535214XA CN201210535214A CN103000867A CN 103000867 A CN103000867 A CN 103000867A CN 201210535214X A CN201210535214X A CN 201210535214XA CN 201210535214 A CN201210535214 A CN 201210535214A CN 103000867 A CN103000867 A CN 103000867A
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Abstract
The invention relates to a graphite composite material with high energy density. The composite graphite material comprises artificial graphite, natural graphite and a coating. A mass ratio of the artificial graphite to the natural graphite is 15:1-1:5; a mass ratio of the coating to the composite graphite is 1:5 to 5:1; the composite graphite comprises the artificial graphite and the natural graphite; the coating material is one selected from middle-temperature coal pitch, high temperature coal pitch, secondary coal pitch, petroleum pitch and coal tar, and a combination thereof. The composite graphite negative electrode material provided by the invention has advantages of high energy density, high discharge capacity, high first discharge (388mAh/g), high first efficiency (higher than 95%), high compactness (1.79g/cm<3>) and good processing performance, and meets requirements of high energy density of lithium ion battery material by portable electronic products.
Description
Technical field
the present invention relates to the lithium ion battery material field, be specifically related to a kind of composite graphite negative electrode material and preparation method thereof and its application of high-energy-density.
Background technology
from Sony corporation of Japan in 1991 successfully by material with carbon element for the preparation of lithium ion battery negative since, the research of relevant carbon negative electrode material of lithium ion cell just receives much concern.In recent years, carbon negative electrode material of lithium ion cell is extensive use in various portable type electronic products (as notebook computer, mobile phone, camera etc.) and communication tool, and the fast development of these emerging fields need to have that volume is little, capacity is high and the miniaturization and of the excellent properties such as energy density is high, be beneficial to the novel battery of environmental protection.
lithium ion battery is as a kind of novel rechargeable battery, has that operating voltage is high, specific energy large, the discharge potential curve is steady, self discharge is little, has extended cycle life, cryogenic property is good, energy density is high, environmental protection, the advantage such as pollution-free, memoryless.One of preparation key technology of lithium ion battery is selection and the research of negative material, and the quality of negative material directly affects the chemical property of battery.
at present, Carbon Materials has become business-like lithium ion battery negative material.The graphite negative electrodes material has that cycle efficieny is high, cycle performance well, lower lithium embeds/takes off embedding current potential, suitable reversible capacity, aboundresources, the advantage such as cheap, and become desirable lithium ion battery negative material.But, graphite type material has layer structure or sclay texture more, graphite layers is with weak Van der Waals force combination, easily cause the embedding of solvation lithium ion and the common insertion of solvent molecule when discharging and recharging, can produce between layers and peel off and form new surface, organic electrolyte continuous reduction decomposition on the new surface formed forms new SEI film, both consumed a large amount of lithium ions, strengthened irreversible capacity loss first, and due to the embedding of solvation lithium ion with deviate to cause volumetric expansion and the contraction of graphite granule, cause intergranular energising network portion to be interrupted, thereby occur affecting its stability because of the distinctive layer structure of graphite type material or sclay texture, cycle performance and security performance.In addition, the lithium storage content of graphite type material is lower, and theoretical specific capacity only has 372 mAh/g, and has first the defects such as discharging efficiency is low, extremely sensitive and selectivity is high to electrolyte, and its application is restricted.Wherein, native graphite has high, the good voltage platform of specific capacity, aboundresources, low cost and other advantages, but has the defects such as irreversible capacity is large first, compacted density is low; It is high that Delanium has structural stability, and embedding lithium function admirable, have extended cycle life, the advantages such as pole piece good processability, but have the defects such as price is high, specific capacity is low.For this reason, be badly in need of graphite type material is carried out to modification (comprising that pattern shaping or pyrolysis coat processing etc.), structural adjustment or development of new negative material, to improve the chemical property of lithium ion battery.
hard carbon claims again difficult graphitized charcoal, by high molecular polymer (as furfural resin, phenolic resins etc.), 1000 ℃ of left and right pyrolysis, is obtained, and is formed by the direct charing of solid phase, and also be difficult to graphitization under the hot conditions higher than 2500 ℃.Hard carbon is a kind of amorphous carbon material, and degree of crystallinity is low, and crystal face is apart from large, good with the compatibility of electrolyte, doubly forthright good with cryogenic property.Hard carbon cathode material has that specific capacity is high, charge-discharge performance and high rate performance good, be beneficial to fast charging and discharging, aboundresources, clean environment firendly, the advantage such as with low cost, can meet the requirement of electrokinetic cell anticathode material high power capacity, long-life, fast charging and discharging.But, hard carbon cathode material exist first charge-discharge efficiency low (being only 45% left and right), first irreversible capacity greatly, the defect such as low, the voltage delay of efficiency, preparation relative complex difficulty first.
soft carbon claims again easy graphitized carbon, the transition state carbon of a kind of amorphous carbon to graphite, as by charings such as petroleum asphalt, coal tar pitch, petroleum cokes, along with temperature is elevated to 2600 ℃ from 300 ℃, the unordered microstructure of these soft material with carbon elements is tending towards ordered arrangement, gradate as graphite-structure forms as Delanium, and degree of graphitization reaches more than 95%.And the microstructure of soft carbon has larger storage lithium ability, and has the theoretical capacity higher than graphite type material and excellent cryogenic property, and there is the advantages such as good cycle, high rate performance be excellent, but there is the defects such as capacity is low, processing characteristics is not good.
needle coke be a kind of impurity content seldom, there is lower resistance and thermal coefficient of expansion, and the very high easy graphitized carbon of its anisotropic degree, mainly comprise two kinds of petroleum needle coke and coal-based needle cokes.
what MCMB (MCMB) was Delanium is a kind of, spherical in shape or subsphaeroidal, react the middle transformation mutually of generation by the compound that contains condensed-nuclei aromatics (as mink cell focus, coal tar pitch, petroleum asphalt, mid temperature pitch, secondary coal tar pitch, naphthalene, residual oil, coal tar, secondary petroleum heavy oil, carbolineum, polycyclic aromatic hydrocarbon etc.) by thermal polycondensation and make.MCMB has good chemical stability, thermal stability, conductivity and thermal conductivity etc., and there is self-adhesive, purity is high, particle diameter is even, high, the rub resistance of hardness after compression molding, and become the high-quality presoma for preparing the high-performance carbon material.
in order to improve the chemical property of carbon negative pole material, overcome the defect that native graphite and Delanium exist separately, multipair graphite material carries out carbon and coats processing, to improve its surface nature, and then improves the chemical property of material.
a kind of modified natural graphite material used in lithium ion battery negative electrodes is disclosed, after described modified graphite cathode material adopts boracic hard carbon layer coated natural graphite, adopt again soft carbon to coat, obtain having the natural graphite negative electrode material of nucleocapsid structure, wherein, the kernel of nucleocapsid structure is native graphite, is coated on the outer field shell of kernel and is comprised of inner casing and shell, inner casing is the boracic hard carbon layer, and shell is soft carbon-coating.Boron element add at high temperature catalyzed graphitization, to improve the structure of hard carbon, greatly improve its ordering degree, can also reduce graphitization temperature, cut down finished cost.Soft carbon coats the specific area that can reduce after hard carbon coats, and improves efficiency first.The preparation method of this modified natural graphite negative material comprises the steps: 1) after being dissolved in to organic solvent, the hard carbon presoma adds boron-containing solution, add native graphite after stirring, fully mix, decompression steams solvent and water, be warming up to 600-1000 ℃ of insulation 1-5 hour, after being down to room temperature, pulverize, sieve; 2) screenings and soft carbon matrix precursor fully mix, and under nitrogen or argon gas atmosphere protection, are warming up to 2500-3000 ℃ and carry out graphitization insulation 1-5 hour, after being down to room temperature, pulverize, sieve, and obtain.The advantage such as this natural graphite negative electrode material has that specific area is little, tap density is high, efficiency is high first, specific capacity is high, good cycle, high rate performance are good, but its preparation process is numerous and diverse, manufacturing cost is higher, the compacted density of negative material powder has much room for improvement.
a kind of composite carbon negative electrode material of lithium ion power battery is disclosed, described carbon negative pole material combines by binding agent or the composite graphite particles of combination, and be dispersed with additive on the composite graphite particles surface, wherein, described additive is selected from as electric conducting materials such as conductive black, acetylene black, gas-phase growth of carbon fibre, carbon nano-tube or nano-sized carbon microballoons.After the preparation method of this carbon negative pole material comprises the steps: the mixed powder of Delanium and native graphite, binding agent, additive are evenly mixed, granulation, extrusion modling, roasting, dipping, charing or graphitization processing, pulverize, and obtains.The composite carbon negative polar material that the document makes has large multiplying power discharging property, fast charging and discharging performance and good cycle performance, is applicable to being applied to electrokinetic cell.But add conductive agent and can increase its production cost, roasting, impregnating step make preparation process numerous and diverse, significant prolongation the production cycle, increased manufacturing cost.
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Summary of the invention
the object of the present invention is to provide a kind of composite graphite negative electrode material of high-energy-density, described composite graphite negative electrode material is comprised of Delanium, native graphite and coating, wherein, the mass ratio of Delanium and native graphite is 15:1-1:5, the mass ratio of coating and composite graphite is 1:5-5:1, described composite graphite is comprised of Delanium and native graphite, and described coating is selected from any or its combination of medium temperature coal pitch, coal tar pitch, secondary coal tar pitch, petroleum asphalt, coal tar.
in the preferred technical solution of the present invention, the mass ratio of coating and composite graphite is 1:3-2:1.
in the preferred technical solution of the present invention, in described composite graphite negative electrode material, the mass ratio of Delanium and native graphite is 12:1-1:3, is preferably 10:1-1:1.
in the preferred technical solution of the present invention, that the grain shape of described Delanium and/or native graphite is selected from is spherical, subsphaeroidal, oval, needle-like, tabular, fibrous, lepidiod any or its combination, is preferably spherical, subglobose any or its combination.
in the preferred technical solution of the present invention, described Delanium is selected from any or its combination of petroleum needle coke, coal-based needle coke, MCMB.
in the preferred technical solution of the present invention, described native graphite is selected from any or its combination of natural flake graphite, micro crystal graphite.
in the preferred technical solution of the present invention, the meta particle diameter (D of described Delanium and/or native graphite
50
) be 1-80 μ m, be preferably 10-70 μ m, more preferably 20-50 μ m.
in the preferred technical solution of the present invention, the compacted density of described composite graphite negative electrode material is 1.60-1.85g/cm
3
, be preferably 1.70-1.80 g/cm
3
.
in the preferred technical solution of the present invention, the D of described composite graphite negative electrode material
50
for 10-30 μ m, be preferably 15-25 μ m.
the defects such as the capacity that the present invention is directed to Delanium existence cycle performance low, that native graphite exists is poor, after Delanium, native graphite are evenly mixed according to the certain mass ratio, with the coating kneading, compression molding again, after the charing black lead processing, pulverize, make a kind of lithium ion battery composite graphite negative electrode material of high-energy-density, described composite graphite negative electrode material has that energy density is high, discharge capacity is high, efficiency is high first, compacted density is high and the advantage such as good processability, has met the requirement of lithium ion battery to the material high-energy-density.
another object of the present invention is to provide a kind of preparation method of composite graphite negative electrode material of high-energy-density, described composite graphite negative electrode material is by Delanium, native graphite and coating form, wherein, the mass ratio of Delanium and native graphite is 15:1-1:5, the mass ratio of coating and composite graphite is 1:5-5:1, described composite graphite is comprised of Delanium and native graphite, described coating is selected from medium temperature coal pitch, coal tar pitch, the secondary coal tar pitch, petroleum asphalt, any of coal tar or its combination, it is characterized in that, comprise the steps:
(1) take Delanium and the native graphite of aequum, by its even mixing, make all mixed things of composite graphite;
(2) coating is joined to composite graphite and all mix in thing, under normal pressure and 100-200 ℃ of condition, carry out kneading to evenly, make and pinch mixed thing;
(3) will pinch mixed thing compression molding under the 50-150Mpa pressure condition, making density is 1.5-1.8 g/cm
3
the mold pressing thing, preferably the mold pressing thing is pane;
(4) under inert gas shielding, the mold pressing thing is carried out to the charing black lead processing under 2500-3000 ℃ of condition, then the charing black lead compound made is pulverized, obtain.
in the preferred technical solution of the present invention, in described composite graphite negative electrode material, the mass ratio of Delanium and native graphite is 12:1-1:3, is preferably 10:1-1:1.
in the preferred technical solution of the present invention, the mass ratio of coating and composite graphite is 1:3-2:1.
in the preferred technical solution of the present invention, that the grain shape of described Delanium and/or native graphite is selected from is spherical, subsphaeroidal, oval, needle-like, tabular, fibrous, lepidiod any or its combination, is preferably spherical, subglobose any or its combination.
in the preferred technical solution of the present invention, described Delanium is selected from any or its combination of petroleum needle coke, coal-based needle coke, MCMB.
in the preferred technical solution of the present invention, described native graphite is selected from any or its combination of natural flake graphite, micro crystal graphite.
in the preferred technical solution of the present invention, the meta particle diameter (D of described Delanium and/or native graphite
50
) be 1-80 μ m, be preferably 10-70 μ m, more preferably 20-50 μ m.
in the preferred technical solution of the present invention, the briquetting pressure in step (3) is 50-120Mpa.
the composite graphite negative electrode material that another object of the present invention is to provide high-energy-density of the present invention is for the preparation of the application in lithium ion cell electrode, and preferred described electrode is negative pole.
in order clearly to explain protection scope of the present invention, the present invention defines as follows to term:
delanium of the present invention refers to what burnt series products or organic polymer thing were made through techniques such as artificial heat treatments, such as being selected from petroleum needle coke, coal-based needle coke, MCMB etc.
native graphite of the present invention refers to natural existence the graphite through purifying and processing, such as being selected from natural flake graphite, micro crystal graphite etc.
mCMB of the present invention can prepare according to preparation method well known in the art.As example, can be according to the disclosed method preparation of Chinese patent application CN 1308113A.
needle coke of the present invention can prepare according to preparation method well known in the art.As example, can according to document (in spirit, Chen Laifu, " production of coal-based needle coke ", " colliery modernization " supplementary issue, 2009: the 110-111 page) disclosed method preparation.
micro crystal graphite of the present invention is again amorphous graphite powder, amorphous graphite powder or black lead powder, is the aggregate of micro crystal graphite, and the overwhelming majority is graphitic carbon, and color is ash just, and metallic luster is arranged, and the diameter of its graphite crystal is generally less than 1 micron, and specific area is 1-5m
2
/ g, only visible its crystalline form under electron microscope.
kneading of the present invention refers in the carbon product preparation method, and the required various charcoal crude granules of batching are stirred at a certain temperature, mix, mediate with coating, makes the technical process of the plasticity thickener mixed.
meta particle diameter (D of the present invention
50
) the cumulative particle sizes percentile that refers to sample corresponding particle diameter while reaching 50%.The present invention adopts laser method and selects MASTERSIZER 2000 analyzers to measure the D50 of material.
particle diameter of the present invention detects and adopts the MASTERSIZER 2000 type laser particle analyzers of Britain Ma Erwen company to be tested, and index of refraction is 2.6, and distilled water medium wet method is disperseed, ultrasonic-wave assisted dispersion.
electronic scanning of the present invention micro-(SEM) test adopts Rigaku JSM-6700F electronic scanner microscope to observe the aspects such as the surface topography of sample, granular size, and emitting voltage is 5KV, and powder surface is carried out to vacuum metal spraying 2min.Wherein, the high-power electron beam that scanning electron microscopy obtains gathering scans on sample, inspire various physical signallings, comprise secondary electron, times scattered electron, transmitted electron, absorption electronics, visible ray and X ray etc., and the reception by these signals, amplify and be shown as picture and analytical sample, obtain the various information of sample topography.
crystal structure of the present invention detects the X-ray diffraction analysis method that adopts, and the Cu-Ka radiation source is used in this XRD test, Guan Liuwei 40mA, and pipe is pressed as 40KV, 12 °/min of sweep speed, sweep limits 10-90 °, step-length is 0.020 °.
the present invention is assembled into simulated battery by composite graphite negative electrode material and its contrast negative material, carries out the charge-discharge performance test.Wherein, the making of simulated battery comprises the steps: according to composite graphite negative electrode material: the mass ratio of conductive carbon black: PVDF is that 90:5:5 takes required composite graphite negative electrode material: conductive carbon black: PVDF, composite graphite negative electrode material and conductive carbon black are ground it is mixed in mortar, to all mix again in 1-METHYLPYRROLIDONE (NMP) solution that thing joins PVDF, stir, make slurry, then slurry is coated on Copper Foil, pole piece is made in drying, roll extrusion.By metal lithium sheet, do electrode, Celgard2400 is barrier film, 1mol/L LiPF6/EC(ethylene carbonate)+DMC(dimethyl carbonate)+EMC(methyl ethyl carbonate fat) (volume ratio 1: 1: 1) is electrolyte, be assembled into simulated battery in the glove box of logical argon gas, carry out electrochemical property test after standing 12h.
the present invention adopts LAND CT2001A battery test system to carry out the constant current charge-discharge test to simulated battery, and the voltage tester scope is 0-1.8V.
first discharge specific capacity of the present invention=with the electric current of 0.2C, be discharged to first the discharge capacity of 0V/active material quality.
initial charge specific capacity of the present invention=with the electric current initial charge of 0.2C is to the discharge capacity of 1.8V/active material quality.
efficiency first of the present invention=(initial charge capacity/discharge capacity) first * 100%.
powder body compacted density of the present invention adopts the test of CARVER powder-compacting machine, wherein, and the volume of the quality/specimen of powder body compacted density=specimen; Compacted density=(negative plate quality-Copper Foil quality)/(thickness after pole piece area * pole piece compacting).
except as otherwise noted, while the present invention relates to the percentage between liquid and liquid, described percentage is volume/volume percentage; While the present invention relates to the percentage between liquid and solid, described percentage is volume/weight percentage; While the present invention relates to the percentage between solid and liquid, described percentage is weight/volume percent; All the other are weight/percentage by weight.
compared with prior art, the present invention has following advantage:
1, after the present invention evenly mixes Delanium, native graphite according to the certain mass ratio, with the coating kneading, after compression molding, again through the charing black lead processing, pulverize, obtain.Composite graphite negative electrode material of the present invention has that energy density is high, discharge capacity is high, discharge first high (reaching 388 mAh/g), first efficiency high (reaching more than 95%), compacted density is high (reaches 1.79g/cm
3
) and the advantage such as good processability, met the requirement of portable type electronic product to the lithium ion battery material high-energy-density;
2, the preparation technology of the composite graphite negative electrode material of high-energy-density of the present invention is simple, easy to operate, is applicable to large-scale industrialization production.
The accompanying drawing explanation
fig. 1 embodiment of the present invention 1 prepares the SEM figure (enlargement ratio 1000) of negative material.
fig. 2 embodiment of the present invention 1 prepares the XRD figure of negative material.
fig. 3 embodiment of the present invention 1 prepares the charging and discharging curve of negative material.
Embodiment
illustrate the present invention below with reference to embodiment, embodiments of the invention are only for technical scheme of the present invention is described, and non-limiting essence of the present invention.
embodiment 1the preparation of composite graphite negative electrode material of the present invention
the preparation method of composite graphite negative electrode material of the present invention, comprise the steps:
(1) take 50Kg D
50
be petroleum coke and the 50Kg D of 25 μ m
50
be the native graphite of 18 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) the 50Kg medium temperature coal pitch is heated to 100 ℃, then by the composite graphite that makes all mixed thing join in the medium temperature coal pitch of 100 ℃, carry out kneading under normal pressure and 100 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) compression molding is for being of a size of the pane of 5cm * 2cm * 2cm under the 60Mpa pressure condition will to pinch mixed thing, and making density is 1.51 g/cm
3
the mold pressing thing;
(4) under nitrogen protection, the pane of mold pressing thing is warmed up to 900 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2500 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the charing black lead compound;
(5) the charing black lead compound first is ground into to the bulky grain powder with impact grinder, then uses ultra-fine pulverizer disintegrating, obtain D
50
it is the composite graphite negative electrode material of the high-energy-density of 17.9 μ m.
embodiment 2the preparation of composite graphite negative electrode material of the present invention
the preparation method of composite graphite negative electrode material of the present invention, comprise the steps:
(1) take 100Kg D
50
be coal-based needle coke and the 50Kg D of 20 μ m
50
be the native graphite of 15 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) the 150Kg medium temperature coal pitch is heated to 100 ℃, then by the composite graphite that makes all mixed thing join in the medium temperature coal pitch of 100 ℃, carry out kneading under normal pressure and 100 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) compression molding is for being of a size of the pane of 5cm * 2cm * 2cm under the 80Mpa pressure condition will to pinch mixed thing, and making density is 1.56 g/cm
3
the mold pressing thing;
(4) under nitrogen protection, the pane of mold pressing thing is warmed up to 950 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2700 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the charing black lead compound;
(5) adopt impact grinder to be ground into the bulky grain powder graphite block after graphitization, then pulverize with airslide disintegrating mill, obtain D
50
it is the composite graphite negative electrode material of the high-energy-density of 17.2 μ m.
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embodiment 3the preparation of composite graphite negative electrode material of the present invention
the preparation method of composite graphite negative electrode material of the present invention, comprise the steps:
(1) take 200Kg D
50
be MCMB and the 50Kg D of 28 μ m
50
be the native graphite of 18 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) the 125Kg coal tar pitch is heated to 120 ℃, then by the composite graphite that makes all mixed thing join in the coal tar pitch of 120 ℃, carry out kneading under normal pressure and 120 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) compression molding is for being of a size of the pane of 5cm * 2cm * 2cm under the 90Mpa pressure condition will to pinch mixed thing, and making density is 1.60 g/cm
3
the mold pressing thing;
(4) under nitrogen protection, the pane of mold pressing thing is warmed up to 950 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2800 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the charing black lead compound;
(5) the charing black lead compound first is ground into to the bulky grain powder with impact grinder, then pulverizes with airslide disintegrating mill, obtain D
50
it is the composite graphite negative electrode material of the high-energy-density of 17.6 μ m.
embodiment 4the preparation of composite graphite negative electrode material of the present invention
the preparation method of composite graphite negative electrode material of the present invention, comprise the steps:
(1) take 300Kg D
50
be MCMB and the 50Kg D of 32 μ m
50
be the native graphite of 20 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) the 350Kg coal tar pitch is heated to 130 ℃, then by the composite graphite that makes all mixed thing join in the coal tar pitch of 130 ℃, carry out kneading under normal pressure and 130 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) compression molding is for being of a size of the pane of 5cm * 2cm * 2cm under the 100Mpa pressure condition will to pinch mixed thing, and making density is 1.65 g/cm
3
the mold pressing thing;
(4) under nitrogen protection, the pane of mold pressing thing is warmed up to 950 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2800 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the charing black lead compound;
(5) the charing black lead compound first is ground into to the bulky grain powder with impact grinder, then pulverizes with airslide disintegrating mill, obtain D
50
it is the composite graphite negative electrode material of the high-energy-density of 17.3 μ m.
embodiment 5the preparation of composite graphite negative electrode material of the present invention and test
the preparation method of composite graphite negative electrode material of the present invention, comprise the steps:
(1) take 400Kg D
50
be MCMB and the 50Kg D of 32 μ m
50
be the native graphite of 25 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) 400Kg oil coal tar pitch is heated to 110 ℃, then by the composite graphite that makes all mixed thing join in the petroleum asphalt of 110 ℃, carry out kneading under normal pressure and 110 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) compression molding is for being of a size of the pane of 5cm * 2cm * 2cm under the 120Mpa pressure condition will to pinch mixed thing, and making density is 1.78 g/cm
3
the mold pressing thing;
(4) under nitrogen protection, the pane of mold pressing thing is warmed up to 950 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2800 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the charing black lead compound;
(5) adopt impact grinder to be ground into the bulky grain powder graphite block after graphitization, then pulverize by ultra-fine ball mill, obtain D
50
it is the composite graphite negative electrode material of the high-energy-density of 18.1 μ m.
embodiment 6the preparation of composite graphite negative electrode material of the present invention and test
the preparation method of composite graphite negative electrode material of the present invention, comprise the steps:
(1) take 50Kg D
50
be MCMB and the 100Kg D of 25 μ m
50
be the native graphite of 15 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) 200Kg oil coal tar pitch is heated to 110 ℃, then by the composite graphite that makes all mixed thing join in the oil coal tar pitch of 110 ℃, carry out kneading under normal pressure and 110 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) compression molding is for being of a size of the pane of 5cm * 2cm * 2cm under the 120Mpa pressure condition will to pinch mixed thing, and making density is 1.74 g/cm
3
the mold pressing thing;
(4) under nitrogen protection, the pane of mold pressing thing is warmed up to 950 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2800 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the charing black lead compound;
(5) the charing black lead compound first is ground into to the bulky grain powder with impact grinder, then pulverizes by ultra-fine ball mill, obtain D
50
it is the composite graphite negative electrode material of the high-energy-density of 18.4 μ m.
embodiment 7the preparation of composite graphite negative electrode material of the present invention and test
the preparation method of composite graphite negative electrode material of the present invention, comprise the steps:
(1) take 50Kg D
50
be MCMB and the 150Kg D of 30 μ m
50
be the native graphite of 20 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) the 200Kg medium temperature coal pitch is heated to 120 ℃, then by the composite graphite that makes all mixed thing join in the medium temperature coal pitch of 120 ℃, carry out kneading under normal pressure and 120 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) compression molding is for being of a size of the pane of 5cm * 2cm * 2cm under the 120Mpa pressure condition will to pinch mixed thing, and making density is 1.72 g/cm
3
the mold pressing thing;
(4) under nitrogen protection, the pane of mold pressing thing is warmed up to 950 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2800 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the charing black lead compound;
(5) the charing black lead compound first is ground into to the bulky grain powder with impact grinder, then pulverizes by ultra-fine ball mill, obtain D
50
it is the composite graphite negative electrode material of the high-energy-density of 17.0 μ m.
embodiment 8the preparation of composite graphite negative electrode material of the present invention and test
the preparation method of composite graphite negative electrode material of the present invention, comprise the steps:
(1) take 50Kg D
50
be MCMB and the 150Kg D of 35 μ m
50
be the native graphite of 30 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) 300Kg secondary coal tar pitch is heated to 120 ℃, then by the composite graphite that makes all mixed thing join in the secondary coal tar pitch of 120 ℃, carry out kneading under normal pressure and 120 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) compression molding is for being of a size of the pane of 5cm * 2cm * 2cm under the 100Mpa pressure condition will to pinch mixed thing, and making density is 1.62 g/cm
3
the mold pressing thing;
(4) under nitrogen protection, the pane of mold pressing thing is warmed up to 950 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2800 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the charing black lead compound;
(5) the charing black lead compound first is ground into to the bulky grain powder with impact grinder, then pulverizes by ultra-fine ball mill, obtain D
50
it is the composite graphite negative electrode material of the high-energy-density of 16.9 μ m.
comparative Examples 1
the preparation method of composite graphite negative electrode material, comprise the steps:
(1) take 50Kg D
50
be MCMB and the 25Kg D of 25 μ m
50
be the native graphite of 18 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) 100Kg petroleum asphalt is heated to 110 ℃, then by the composite graphite that makes all mixed thing join in the petroleum asphalt of 110 ℃, carry out kneading under normal pressure and 110 ℃ of conditions, even to kneading, make and pinch mixed thing;
(3) under nitrogen protection, the kneading thing is warmed up to 950 ℃ with the speed of 2 ℃/min and processes 3h, then be warmed up to 2800 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain the graphite clad material.
comparative Examples 2
the preparation method of composite graphite negative electrode material, comprise the steps:
(1) take 50Kg D
50
be MCMB and the 100Kg D of 22 μ m
50
be the native graphite of 15 μ m, it is inserted in mixer it is mixed, make all mixed things of composite graphite;
(2) under nitrogen protection, by composite graphite all mixed thing be warmed up to 950 ℃ with the speed of 2 ℃/min and process 3h, then be warmed up to 2800 ℃ with the speed of 1.5 ℃/min and carry out graphitization processing 6h, obtain admixed graphite;
test examplethe charge-discharge performance test of composite graphite negative electrode material
this test example adopts following method that the composite graphite negative electrode material of embodiment 1-8 and Comparative Examples 1-2 is assembled into to simulated battery, then carries out the charge-discharge performance test.
the making of simulated battery comprises the steps: according to composite graphite negative electrode material: the mass ratio of conductive carbon black: PVDF is that 90:5:5 takes required composite graphite negative electrode material: conductive carbon black: PVDF, composite graphite negative electrode material and conductive carbon black are ground it is mixed in mortar, make all mixed things; To all mix again in 1-METHYLPYRROLIDONE (NMP) solution that thing joins PVDF, stir, make slurry; Slurry is coated on Copper Foil, pole piece is made in drying, roll extrusion again.By metal lithium sheet, do electrode, Celgard2400 is barrier film, 1mol/L LiPF6/EC(ethylene carbonate)+DMC(dimethyl carbonate)+EMC(methyl ethyl carbonate fat) (volume ratio 1: 1: 1) is electrolyte, be assembled into simulated battery in the glove box of logical argon gas, carry out electrochemical property test after standing 12h.
adopt LAND CT2001A battery test system to carry out the constant current charge-discharge test to simulated battery, the voltage tester scope is 0-1.8V.Experimental result is in Table 1.
the performance test results of table 1 composite graphite negative electrode material of the present invention
from table 1, after the present invention evenly mixes Delanium, native graphite according to the certain mass ratio, with the coating kneading, compression molding is by the charing black lead processing, pulverize, it is high that the lithium ion battery composite graphite negative electrode material made has discharge capacity, and electric discharge first reaches 388 mAh/g, efficiency high (more than 95%), the high (1.79g/cm of powder-compacting first
3
) and the advantage such as good processability, met the requirement of portable type electronic product to the lithium ion battery material high-energy-density.The preparation technology of the composite graphite negative electrode material of high-energy-density of the present invention is simple, easy to operate, is applicable to large-scale industrialization production.
Claims (10)
1. the composite graphite negative electrode material of a high-energy-density, described composite graphite negative electrode material is comprised of Delanium, native graphite and coating, wherein, the mass ratio of Delanium and native graphite is 15:1-1:5, the mass ratio of coating and composite graphite is 1:5-5:1, described composite graphite is comprised of Delanium and native graphite, and described coating is selected from any or its combination of medium temperature coal pitch, coal tar pitch, secondary coal tar pitch, petroleum asphalt, coal tar.
2. composite graphite negative electrode material according to claim 1, in described composite graphite negative electrode material, the mass ratio of coating and composite graphite is 1:3-2:1.
3. according to the described composite graphite negative electrode material of claim 1-2 any one, in described composite graphite negative electrode material, the mass ratio of Delanium and native graphite is 12:1-1:3, is preferably 10:1-1:1.
4. according to the described composite graphite negative electrode material of claim 1-3 any one, that the grain shape of described Delanium and/or native graphite is selected from is spherical, subsphaeroidal, oval, needle-like, tabular, fibrous, lepidiod any or its combination, is preferably spherical, subglobose any or its combination.
5. according to the described composite graphite negative electrode material of claim 1-4 any one, the D of described Delanium and/or native graphite
50for 1-80 μ m, be preferably 10-70 μ m, more preferably 20-50 μ m.
6. according to the described composite graphite negative electrode material of claim 1-5 any one, the compacted density of described composite graphite negative electrode material is 1.60-1.85g/cm
3, be preferably 1.70-1.80 g/cm
3.
7. according to the described composite graphite negative electrode material of claim 1-6 any one, the D of described composite graphite negative electrode material
50for 10-30 μ m, be preferably 15-25 μ m.
8. the preparation method of the composite graphite material of the described high-energy-density of claim 1-7 any one, described composite graphite material is comprised of Delanium, native graphite and coating, wherein, the mass ratio of Delanium and native graphite is 15:1-1:5, the mass ratio of coating and composite graphite is 1:5-5:1, described composite graphite is comprised of Delanium and native graphite, described coating is selected from any or its combination of medium temperature coal pitch, coal tar pitch, secondary coal tar pitch, petroleum asphalt, coal tar, it is characterized in that, comprise the steps:
Take Delanium and the native graphite of aequum, by its even mixing, make all mixed things of composite graphite;
Coating is joined to composite graphite and all mix in thing, under normal pressure and 100-200 ℃ of condition, carry out kneading to evenly, make and pinch mixed thing;
To pinch mixed thing compression molding under the 50-150Mpa pressure condition, making density is 1.5-1.8 g/cm
3the mold pressing thing, preferably the mold pressing thing is pane;
Under inert gas shielding, the mold pressing thing is carried out to the charing black lead processing under 2500-3000 ℃ of condition, then the charing black lead compound made is pulverized, obtain.
9. preparation method according to claim 8, the briquetting pressure in step (3) is 50-120Mpa.
10. the composite graphite material of the high-energy-density that the composite graphite material of the described high-energy-density of claim 1-7 any one or the described preparation method of claim 8-9 any one make is for the preparation of the application in lithium ion cell electrode, and preferred described electrode is negative pole.
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