CN104681786A - Coal-based anode material, preparation method and lithium-ion battery - Google Patents
Coal-based anode material, preparation method and lithium-ion battery Download PDFInfo
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Abstract
The invention discloses a coal-based anode material, a preparation method and a lithium-ion battery. The coal-based anode material consists of a coal-based material graphitized inner layer, a middle layer and an outer layer distributed on the surface. The preparation method of the coal-based anode material comprises steps as follows: crushing a coal-based material; then adding a binder or mixing the binder and a modifier; then performing pressing and high-temperature graphitization to form a finished product. The coal-based anode material adopts a stable graphite structure, the surface has good compatibility with an electrolyte, and the coal-based anode material has the high specific capacity, the high conductivity, the high rate capability as well as excellent electrolyte absorbing performance and cycle performance. According to the preparation method, the anode material is prepared from the low-price coal-based material used as a raw material, the technology is simple, industrialization is easy to realize, and meanwhile, the application of the coal-based anode material in the field of the lithium-ion battery is promoted.
Description
Technical field
The invention belongs to field of lithium ion battery, particularly the coal-based negative material of one, preparation method and lithium ion battery.
Background technology
Lithium ion battery is now by everybody extensive use, and conventional small lithium ion battery will present the trend of steady growth under the drive of panel computer and super, and electrokinetic cell and energy-storage battery will be lithium ion battery industry new growth points.Lithium ion battery graphite negative electrodes material is generally be prepared from by native graphite or petroleum coke or coal tar, its structure be carbon atom by hexagonal ring shape arrangement stratification, there is good embedding lithium performance.And coal especially anthracite as carbon materials, its main component is carbon, wherein aromatic structure/molecular chaperones occupies larger proportion, and these aromatic structures or aromatic molecules also can be converted into graphite material under suitable condition, is a kind of desirable raw material preparing high graphitization degree graphite products.Therefore, be the problem that the research that the coal-based negative material of lithium ion battery prepared by raw material has also become at present numerous researcher and pays close attention to based on coal.
At present, the lithium ion battery research of coal-based negative material, mainly take to be that the deliming (purifying) of coal feedstock is high temperature modified afterwards obtain, the ash removal from raw coal process of people's researchs such as coal conversion National Key Laboratory of Shanxi Coal-Chemical Inst., Chinese Academy of Sciences of China Li Baohua mainly adopts the chemical purification of mixed acid, ash element is dissolved in strong acid, purer coal-based negative material (Study on carbon prepared from coal as anode for lithium ion battery is obtained by filtering cleaning method, Ningxia University's journal, June calendar year 2001,22nd volume the 2nd phase, 229-230); The too western coal deliming process of people's research such as to meet during Materials Science and Engineering system of Tsing-Hua University, the mode of main employing high temperature graphitization, ash element is at high temperature volatilized, and then obtain purer coal-based carbon negative material (the graphitization modification of too western coal and lithium ion battery negative performance thereof, coal journal, in November, 2012, the 37th volume o. 11th, 1925-1929); In addition, the people such as the China Mining University Wang Yu tinkling of pieces of jade study in great detail with regard to the ultrapure preparation technology of anthracite and equipment, obtain ultrapure coal product, (the ultrapure preparation technology of Taixi anthracite studies with equipment to have good techno-economic effect, China Mining University's thesis for the doctorate, in September, 2009).
But in the acidifying deliming process of routine, the use of acid easily causes potential safety hazard, and to environment.The materials processing poor performance that conventional high temperature graphitization is produced, capacity and efficiency lower, and the poor compatibility of electrolyte, cycle performance is poor.So exploitation high power capacity, high efficiency, good processability, electrolyte compatibility coal-based negative material that is good, good cycle are key issues coal being applied to the solution of field of lithium ion battery needs.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of coal-based negative material.It is good that coal-based negative material provided by the invention has structural stability, and good processability, surface and the compatibility of electrolyte are good, has the advantages such as the absorbent of height ratio capacity, high conductivity, high magnification and excellence and cycle performance simultaneously.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A kind of coal-based negative material, be made up of coal-based material graphitization internal layer, intermediate layer and the skin that is distributed in surface, wherein said intermediate layer is formed by permeating binding agent and coal-based material surface binding agent graphitization in coal-based material hole.
As preferably, described skin is obtained after graphitization by binding agent.
The internal layer of described coal-based negative material, intermediate layer and skin respectively by the coal-based material of internal layer, permeate and obtain after graphitization at the binding agent of coal-based material hole and the binding agent of coal-based material surface.As shown in the structural representation (Fig. 1) of coal-based negative material, I layer is internal layer, is obtained after graphitization by coal-based material; II layer is intermediate layer, is mixed to get primarily of the binding agent permeated in coal-based material hole and coal-based material surface binding agent graphitization.
As preferably, the fixed carbon content of described coal-based negative material is>=99.9%, average grain diameter D
50be 2.0 ~ 40.0 μm, specific area is 1.0 ~ 30.0m
2/ g, real density>=2.0g/cc.
Preferably, the interlamellar spacing d of 002 crystal face
002for:
degree of disorder I
d/ I
g(area ratio) is 0.1 ~ 0.5.
Under above-mentioned condition, the reversible specific capacity >=340.0mAh/g of described coal-based negative material, initial coulomb efficiency >=90.0%, 10C/1C Capacity Ratio >=80.0%, 1C discharge and recharge 500 weeks circulation volume conservation rate >=80.0%.
Preferably, described average grain diameter D
50be 3.0 ~ 30.0 μm, specific area is 1.0 ~ 20.0m
2/ g, real density>=2.1g/cc.
Preferably, the interlamellar spacing d of described 002 crystal face
002for
degree of disorder I
d/ I
gbe 0.2 ~ 0.4.
Under optimum condition, the reversible specific capacity >=350.0mAh/g of described coal-based negative material, initial coulomb efficiency >=92.0%, 10C/1C Capacity Ratio >=85.0%, 1C discharge and recharge 500 weeks circulation volume conservation rate >=85.0%.
As preferably, described coal-based negative material is follow-up to its modifying surface, preferably forms the one kind or two or more combination in carbon-coating, inorganic non-metallic simple substance, inorganic non-metallic compound, metal simple-substance, metallic compound on coal-based negative material surface.
Preferably, the modifier of described modification is the one kind or two or more combination in the simple substance of boron, phosphorus, silicon, aluminium or titanium, compound or salt.
Preferably, at least one in coated, mechanical fusion, mechanically modifying, ball milling is modified as described in.
As preferably, described coal-based material is the one kind or two or more combination in anthracite, coking coal, bottle coal, coal-based coke, or anthracite, coking coal, bottle coal, one kind or two or more and graphite in coal-based coke combination.
Preferably, being 0.1%-95.0% containing the mass percent of graphite in the coal-based material of graphite, such as, is 0.5%, 3.0%, 10.0%, 30.0%, 45.0% etc., is preferably 0.1%-50.0%.
Preferably, described graphite is the one kind or two or more combination in native graphite, Delanium or carbosphere.
Preferably, described native graphite is crystalline flake graphite and/or micro crystal graphite.
The typical but non-limiting example of combination of described coal-based material has: anthracite; The combination of anthracite and micro crystal graphite, Delanium; The combination of smokeless coal and coke, crystalline flake graphite; The combination of coking coal and anthracite, coal-based coke, Delanium, carbon microspheres, crystalline flake graphite or micro crystal graphite.
Preferably, described binding agent is the one kind or two or more combination in the organic substances such as pitch, resin, high molecular polymer, acid anhydrides, coal tar, heavy oil, carbolineum.
Two of object of the present invention is the preparation method providing a kind of coal-based negative material of the present invention, comprises and mixing adding binding agent after coal-based material disintegrating; Then described coal-based negative material is namely obtained through die mould, high temperature graphitization.Finished product is can be made into after crushing and screening.The method adopts the coal of low price to be raw material, prepares cathode material of lithium ion battery, and technique is simple, is easy to industrialization, has promoted the application of coal-based negative material in field of lithium ion battery simultaneously.
Preferably, described preparation method comprises and will add binding agent after coal-based material disintegrating and modifier carries out mixing and surface modification treatment; Then described coal-based negative material is namely obtained through die mould, high temperature graphitization.
Preferably, described mixing adopts kneading.
The coal-based negative material tangent plane SEM that the present invention obtains schemes (Fig. 2 A) and TEM schemes (Fig. 2 B) as shown in the figure.Intermediate layer is mixed to get through graphitization primarily of the binding agent permeated in coal-based material hole and coal-based material surface binding agent, in mixed processes, binding agent may penetrate in the hole of raw material, in graphitization temperature-rise period, binding agent can infiltrate in the hole of coal-based material surface further, continues raised temperature, other hetero-atoms in binding agent are removed, start to form six-membered ring structure, remaining carbon atom and coal-based in carbon atom reset and form six-membered ring structure, finally form intermediate layer.
Scheme (in Fig. 2 A) by coal-based negative material tangent plane SEM, under 2.5 thousand times of amplification conditions, the internal layer and skin of seeing coal-based negative material can be known; Can observe by TEM figure (Fig. 2 B), between internal layer (a layer) and outer (c layer), not have obvious signs of delamination, but there is one deck mixing intermediate layer b layer.
As preferably, said method comprising the steps of:
(1) by coal-based material disintegrating to average grain diameter D
50=2.0-40.0 μm;
(2) add in step (1) gained material binding agent or, or binding agent and modifier mix, or carry out mixing and modification;
(3), under protective atmosphere or under purification atmosphere, high temperature graphitization process is carried out to step (2) gained material;
Optionally step (3) gained graphitization product carry out sieving and removing magnetic by (4), obtain coal-based negative material.
As preferred further, said method comprising the steps of:
(1) by coal-based material disintegrating to average grain diameter D
50=2.0-40.0 μm;
(2) add in step (1) gained material binding agent or, or binding agent and modifier carry out kneading, material is implemented to mixing and the extruding of continous way, material is fully mixed;
(3) material after step (2) kneading is carried out forming processes, obtain the die mould product of cylinder and/or packet;
(4), under protective atmosphere or under purification atmosphere, high temperature graphitization process is carried out to die mould product;
Optionally graphitization product are pulverized by (5), screening, obtain coal-based negative material except magnetic.
As preferably, the fixed carbon mass content in described coal-based material is more than 80.0%, such as, be 82.0%, 86.0%, 90.0%, 95.0%, 99.0%, 99.9% etc., be preferably more than 85.0%.
Preferably, described pulverizing be mechanical crushing, air-flow crushing, grind in any a kind.Equipment can select high speed machine impact grinder, beater grinder, tooth-like pulverizer, turbine type crushing machine, pressure mill formula pulverizer, milling type pulverizer, airslide disintegrating mill, ball mill, raymond mill, two rod pulverizers etc.
Preferably, described binding agent accounts for the 0.1%-50.0% of coal-based quality of materials, is preferably 1.0%-40.0%.
Preferably, described modifier accounts for the 0.05%-30.00% of coal-based quality of materials, is preferably 0.10%-25.00%.
As preferably, described graphited equipment adopts any a kind in inner series graphitizing furnace or acheson furnace.
Preferably, described protective atmosphere refers to helium, neon, argon gas, nitrogen or vacuum atmosphere, and purification gas is the one kind or two or more combination of chlorine, freon, fluorine gas.
Preferably, described graphitization temperature is 2800-3400 DEG C, such as, be 2850 DEG C, 3100 DEG C, 3320 DEG C etc.
As preferably, described forming processes adopts compression molding or isostatic compaction.
Preferably, the equipment of described compression molding adopts any a kind in single column hydraulic machine, four-column hydraulic press, horizontal hydraulic machine, vertical hydraulic press or universal hydraulic machine; The equipment of described isostatic compaction adopts any a kind in screw-type cold isostatic press, frame-type cold isostatic press, hot isostatic press.
Preferably, the bulk density of described die mould product is 1.0 ~ 1.6g/cm
3.
As preferably, described mixing or kneading are solid phase mixing or liquid phase mixing.
Preferably, the equipment of described mixing or kneading is any a kind in high speed dispersor, two stirring two heating kneading machine, vacuum kneading machine, V-Mixer, trough type mixing machine, drum mixer, conical twin-screw mixer, dual cone mixer or solid phase fusion machine.
Preferably, the temperature of described mixing or kneading is 10-300 DEG C, such as, be 13 DEG C, 25 DEG C, 80 DEG C, 150 DEG C, 220 DEG C, 280 DEG C.
Preferably, the time of described mixing or kneading is 5-300min.
Preferably, after liquid phase mixing, adopt spray-dired mode to remove solvent, make it fully mix, the temperature of preferably spray drying is 50-350 DEG C.
Three of object of the present invention is to provide a kind of lithium ion battery, containing the coal-based negative material that coal-based negative material of the present invention or preparation method of the present invention obtain in the negative material of described lithium ion battery.Cathode material of lithium ion battery prepared by the present invention, performance index can reach the requirement of lithium ion battery high-energy-density, can be applied in lithium ion battery applications field well.
Preferably, the negative material of described lithium ion battery is made up of described active material and cementitious additives.
Compared with prior art, described coal-based negative material has internal layer, intermediate layer and outer field graphite-structure in the present invention, and surface is good with the compatibility of electrolyte, has height ratio capacity, high efficiency, high rate capability, excellent absorbent and cycle performance.The fixed carbon content of powder can reach more than 99.9%, and real density can at more than 2.1g/cc, interlamellar spacing d
002can be
specific capacity can at more than 350mAh/g, and efficiency can more than 92%, and 10C/1C Capacity Ratio can be more than 85%, the 1C charge and discharge cycles capability retention of 500 weeks can more than 85%.
Preparation method provided by the invention compares with conventional method, preparation technology is simple, do not adopt the operations such as conventional chemical purification, decrease the pollution of chemical purification acid to environment, adopt with brand-new technological process, and process control accurately, without harsh conditions, be easy to industrialization, the powder characteristic of preparation better, can be applied in lithium ion battery applications field.
Accompanying drawing explanation
Fig. 1 is coal-based negative material structural representation prepared by the present invention;
Wherein, I-internal layer, II-intermediate layer, III-is outer;
Fig. 2 is that coal-based negative material tangent plane SEM prepared by the present invention schemes and TEM figure;
Fig. 3 is XRD figure (Si is as interior mark) of coal-based negative material prepared by the embodiment of the present invention 1;
Fig. 4 is the charging and discharging curve figure of coal-based negative material prepared by the embodiment of the present invention 1;
Fig. 5 is the different multiplying discharge curve of coal-based negative material prepared by the embodiment of the present invention 1;
Fig. 6 is the cyclic curve figure of coal-based negative material prepared by the embodiment of the present invention 1.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
Embodiment 1
(1) by fixed carbon content be 80.0% anthracite be crushed to D through milling pin pulverizer
50=13.6 μm;
(2) by above-mentioned powder body material and 2.0% (weight ratio) phosphoric acid and 5.0% epoxy resin at V-Mixer mixing 5min, mixing temperature is 80 DEG C;
(3) put into inner series graphitizing furnace, pass into protective gas nitrogen, graphitization at the temperature of 2800 DEG C;
(4) graphitization product are carried out sieving and removing magnetic, obtain D
50the coal-based negative material of=15.3 μm, other Testing index is in table 3.
Embodiment 2
(1) bottle coal containing fixed carbon content being 99.0% is crushed to D through ball mill
50=20.0 μm;
(2) by above-mentioned powder body material with 10.0% polyvinyl alcohol at conical twin-screw mixer mixing 60min, mixing temperature is 25 DEG C;
(3) material mixed is put into acheson furnace, pass into protective gas nitrogen and purifying gas fluorine gas respectively, graphitization at the temperature of 3000 DEG C;
(4) graphitization product are carried out sieving and removing magnetic, obtain D
50the coal-based negative material of=28.0 μm, other Testing index is in table 3.
Embodiment 3
(1) coking coal containing fixed carbon content being 95.0% is crushed to D through turbine type crushing machine
50=5.0 μm;
(2) by above-mentioned powder body material and the pitch of 30.0% and the titanium dioxide of 5.0%, at conical twin-screw mixer mixing 60min, mixing temperature is 120 DEG C;
(3) the material horizontal hydraulic machine mixed being pressed into bulk density is 1.0g/cm
3square; Square stampings are put into acheson furnace, passes into purifying gas chlorine, graphitization at the temperature of 3200 DEG C;
(4) graphitization square product are crushed to D
50=5.8 μm, sieve, except magnetic obtains coal-based negative material, other Testing index is in table 3.
Embodiment 4
(1) anthracite containing fixed carbon content being 85.0% is crushed to D through pressure mill formula pulverizer
50=15.0 μm; By fixed carbon content be 99.9% crystalline flake graphite pressure mill formula pulverizer be crushed to D
50=7.8 μm; By the anthracite crushed and the ratio solid phase mixing 30min of the crystalline flake graphite crushed according to 50.0:50.0;
(2) by above-mentioned mixed powder material and the polyacrylonitrile of 20.0% and the alundum (Al2O3) of 0.5%, kneading 120min in the two heating kneading machine of two stirring;
(3) the material universal hydraulic machine mixed being pressed into bulk density is 1.3g/cm
3cylindrical piece;
(4) cylindrical piece is put into inner series graphitizing furnace, graphitization at the temperature of 3300 DEG C;
(5) graphited cylindrical piece is crushed to D
50=11.4 μm, screening, except magnetic, obtain, coal-based negative material, other Testing index is in table 3.
Embodiment 5
(1) coke containing fixed carbon content being 99.0% is crushed to D through high speed machine impact grinder
50=7.8 μm;
(2) by the coke that crushes and D
50=15.0 μm of carbospheres are according to the ratio solid phase mixing 30min of 50.0:50.0;
(3) by above-mentioned mixed powder material and the polyacrylonitrile of 20.0% and the alundum (Al2O3) of 0.5%, kneading 120min in the two heating kneading machine of two stirring, kneading temperature is 300 DEG C;
(4) material mixed is put into Inner string data graphitizing furnace, graphitization at the temperature of 3300 DEG C;
(5) graphitization product are carried out sieving and removing magnetic, obtain D
50the coal-based negative material of=11.4 μm, other Testing index is in table 3.
Embodiment 6
(1) coking coal containing fixed carbon content being 95.0% is crushed to D through airslide disintegrating mill
50=13.3 μm; By fixed carbon content be 95.0% micro crystal graphite be crushed to D through airslide disintegrating mill
50fixed carbon content is that the Delanium of 99.9% is crushed to D through airslide disintegrating mill by=15.6 μm
50=30.0 μm, D will be crushed to
50coking coal, the D of=13.3 μm
50the Delanium of=30.0 μm and D
50the micro crystal graphite of=15.6 μm, according to 50.0:10.0:40.0 solid phase mixing 10min;
(2) by above-mentioned mixed powder material and the pitch of 10.0%, the carbolineum of 30.0% and the equal benzoic anhydride of 5.0% and boron carbide kneading 300min in vacuum kneading machine of 20.0%, kneading temperature is 150 DEG C;
(3) material mixed being pressed in hot isostatic press bulk density is 1.50g/cm
3square;
(4) square is put into Inner string data graphitizing furnace, at the temperature of 3300 DEG C, carry out graphitization;
(5) graphitization product are crushed to D
50=19.3 μm, sieve, except magnetic obtains coal-based negative material, other Testing index is in table 3.
Embodiment 7
(1) coking coal containing fixed carbon content being 91.0% is crushed to D through airslide disintegrating mill
50=5.0 μm; By fixed carbon content be 80.0% micro crystal graphite be crushed to D through airslide disintegrating mill
50fixed carbon content is that the Delanium of 99.9% is crushed to D through airslide disintegrating mill by=25.6 μm
50=30.0 μm, D will be crushed to
50coking coal, the D of=13.3 μm
50the Delanium of=30.0 μm and D
50the micro crystal graphite of=15.6 μm, according to 5.0:5.0:90.0 solid phase mixing 10min;
(2) by above-mentioned mixed powder material and the equal benzoic anhydride of 0.1% and boron carbide kneading 20min in vacuum kneading machine of 30.0%, kneading temperature is 15 DEG C;
(3) material mixed being pressed in hot isostatic press bulk density is 1.60g/cm
3square;
(4) square is put into Inner string data graphitizing furnace, at the temperature of 2900 DEG C, carry out graphitization;
(5) graphitization product are crushed to D
50=19.3 μm, sieve, except magnetic obtains coal-based negative material, other Testing index is in table 3.
Embodiment 8
(1) coking coal containing fixed carbon content being 83.0% is crushed to D through airslide disintegrating mill
50=2.0 μm; By fixed carbon content be 99.9% Delanium be crushed to D through airslide disintegrating mill
50=20.0 μm, D will be crushed to
50coking coal, the D of=13.3 μm
50the Delanium of=30.0 μm, according to 50.0:50.0 solid phase mixing 10min;
(2) by above-mentioned mixed powder material and the equal benzoic anhydride of 25% and boron carbide kneading 80min in vacuum kneading machine of 0.05%, kneading temperature is 200 DEG C;
(3) material mixed being pressed in hot isostatic press bulk density is 1.20g/cm
3square;
(4) square is put into Inner string data graphitizing furnace, at the temperature of 3050 DEG C, carry out graphitization;
(5) graphitization product are crushed to D
50=19.3 μm, sieve, except magnetic obtains coal-based negative material, other Testing index is in table 3.
Comparative example 1
(1) coking coal containing fixed carbon content being 90.0% is crushed to D through beater grinder
50=15.6 μm;
(2) above-mentioned powder is put into inner series graphitizing furnace, pass into nitrogen, graphitization at the temperature of 3000 DEG C;
(3) graphitization product are carried out sieve, except magnetic, obtain D
50the coal-based negative material of=16.5 μm, other Testing index is in table 3.
Comparative example 2
(1) coke containing fixed carbon content being 80.0% is crushed to D through pressure mill formula pulverizer
50=35.0 μm;
(2) by above-mentioned powder with 10.0% pitch in drum mixer, mix 120min;
(3) material mixed is put into acheson furnace, pass into protective gas nitrogen respectively and pass into purifying gas freon, graphitization at the temperature of 2900 DEG C;
(4) graphitization product are carried out sieve, except magnetic, obtain D
50the coal-based negative material of=38.0 μm, other Testing index is in table 3.
Carry out following performance test to lithium ion battery prepared by embodiment 1 ~ 8 and comparative example 1 ~ 2 with coal-based negative material, test result is in table 3.
(1) surface and internal state:
The surface topography of the coal-based negative material prepared with the present invention of Chinese Branch Tech KYKY-2800B type scanning electron microscope test, as shown in Fig. 2 (A), clearly can see internal layer and the layer structure of coal-based negative material; Test its micromorphology structure by new Experiment of Material Science room, Dongguan transmission electron microscope, can see as Suo Shi Fig. 2 (B) does not have obvious layering vestige between internal layer and skin, but there is one deck intermediate layer.
Adopt coal-based negative material prepared by technological process of the present invention, good processability, not free settling, simultaneously and the compatibility of electrolyte good, the high rate performance had and long circulating performance.
(2) 002 crystal face interlamellar spacing d
002:
With reference to d in GB GB/T 24533-2009 " silicon/carbon/graphite in lithium ion batteries class negative material "
002method of testing, with the test of Holland-PANalytical X'pert PRO X-ray diffractometer, add the Si of 30% as interior mark in powder, concrete data processing is with reference to GB/T 24533-2009, the d of test
002?
between.
(3) purity:
With reference to the method formulated in standard GB/T 212-91 " proximate analysis of coal ", purity >=99.9% of the coal-based negative material of lithium ion battery prepared by test the method for the invention.Described " purity " is defined as fixed carbon content percentage in product.
(4) particle diameter:
Britain Malvern-Mastersizer 2000 type laser particle size analyzer is adopted to test the coal-based negative material average grain diameter of lithium ion battery of the present invention between 2.0 ~ 40.0 μm.
(5) specific area:
Adopt the BET method of nitrogen adsorption, the specific area that Tristar 3000 ratio surface area instrument of U.S. micro tests the coal-based negative material of lithium ion battery prepared by the present invention is 1.0 ~ 40.0m
2/ g.
(6) real density:
The ULTRAPYCNOMETER1000 real density tester of U.S. Kang Ta is adopted to test the real density >=2.0g/cc of the coal-based negative material of lithium ion battery of the present invention;
(7) electrochemical property test:
A, utilize the coal-based negative material of lithium ion battery of the present invention to prepare lithium ion simulated battery, specifically comprise the steps:
1. lithium ion battery negative pole active materials is made with coal-based negative material prepared by the inventive method, carboxyl methyl cellulose is thickener; styrene butadiene rubber sbr is binding agent; conductive agent super P (SP); make electrode material, the mode that three is active material: SP:CMC:SBR=95.5:1.0:1.5:2.0 according to mass ratio mixes.Add appropriate deionized water, mix well into pasty state with paste mixer, solid content is 40.0%-50.0%, and then use coating machine coating on Copper Foil, coating thickness is 200 μm, is punching into the pole piece that diameter is 8.4mm after oven dry.
2. be to electrode with pour lithium slice, above-mentioned pole piece is work electrode, and (positive pole stainless steel gasket diameter is 8.4mm to adopt Celgard 2400 type PE/PP/PE composite diaphragm in German Braun glove box, be assembled into die type; Negative pole copper backing diameter is 11.4mm) simulated battery, H
2o and O
2bias voltage is all lower than 1ppm.Electrolyte adopts the solution of 1M LiPF6/EC+DMC+EMC.
B, use Wuhan gold promise Land CT 2001A charge-discharge test cabinet, in the voltage range of 0.001 ~ 1.500V, carry out the test of simulated battery charge-discharge performance with the current density of segmentation.Method of testing and data are calculated as follows:
Embedding lithium specific capacity first: charge to 0.005V with the current density of 0.1C, then the quality of capacitance/negative electrode active material charging to 0.001V with the current density of 0.02C;
De-lithium specific capacity first: the quality being discharged to the capacitance/negative electrode active material of 1.500V with the current density of 0.1C;
The charge specific capacity of coal-based negative material charge and discharge cycles, specific discharge capacity and efficiency prepared by the embodiment of the present invention 1 are as shown in table 2, and charging and discharging curve as shown in Figures 3 to 5; In figure, charging curve 1, charging curve 2 and charging curve 3 represent the charging curve of circulation in the 1st, 2 and 3 week respectively, and discharge curve 1, discharge curve 2 and discharge curve 3 represent the discharge curve of circulation in the 1st, 2 and 3 week respectively.
The charge and discharge cycles summary table of coal-based negative material prepared by table 2 embodiment 1
| Circulating cycle number | Charge specific capacity (mAh/g) | Specific discharge capacity (mAh/g) | Efficiency (%) |
| 1 | 350.0 | 367.8 | 95.2 |
| 2 | 349.6 | 351.9 | 99.4 |
| 3 | 349.3 | 350.8 | 99.6 |
(8) full Cell Performance Evaluation:
A, utilize the coal-based negative material of lithium ion battery of the present invention to prepare the full battery of lithium ion, specifically comprise the steps:
1. make lithium ion battery negative pole active materials with coal-based negative material prepared by the inventive method, super P (SP) is conductive agent, and styrene butadiene rubber sbr is binding agent, and carboxyl methyl cellulose is that thickener obtains electrode material; The mode being active material: SP:CMC:SBR=95.5:1.0:1.5:2.0 according to mass ratio mixes.Add appropriate deionized water, mix well into pasty state with paste mixer, solid content is 40.0%-50.0%, then adopts coating machine coating on Copper Foil, makes the full battery cathode of lithium ion after vacuumize.
2. with cobalt acid lithium LiCoO
2, lithium nickelate LiNiO
2or spinel lithium manganate LiMn
2o
4for positive electrode; With 1M LiPF
6/ EC+DMC+EMC is electrolyte; With Celgard 2400 type PE/PP/PE composite membrane for barrier film; The production technology of conventional 18650 type cells is adopted to assemble full battery.
B, use Wuhan gold promise Land CT 2001A charge-discharge test cabinet, in the voltage range of 3.0 ~ 4.2V, carry out charge-discharge test with different current densities.Performance evaluation and method of testing as follows:
Battery high rate performance is evaluated: to full battery with 0.5mA/cm
2current density carry out constant current charge, then discharge with the discharging current of 1C, 3C, 5C, 10C respectively, test the discharge capacity change of full battery, and calculate the capability retention of different discharge-rate:
10C/1C represents that 10C multiplying power discharging capacity compares the ratio of 1C multiplying power discharging capacity;
Above-mentioned ratio is larger, illustrates that the capability retention of multiplying power discharging is higher, and the high rate performance of the full battery of 18650 type is better, and the chemical property of described coal-based negative material is better.
The different multiplying discharge curve of coal-based negative material prepared by the embodiment of the present invention 1 and the charge and discharge cycles curve of 1C are as shown in Figure 5, Figure 6.
The physical property of table 3 embodiment and comparative example and electrochemical property test result
The physical property of embodiment 1 ~ 8 and comparative example 1 ~ 2 and the display of electrochemical property test result:
Coal-based negative material in comparative example 1, owing to only pulverizing raw material, does not do other modifications, causes the inadequate stable uniform of the carbonization structure of material, thus capacity and efficiency lower, later cycles poor-performing.
Coal-based negative material in comparative example 2, owing to not controlling particle diameter well, and property-modifying additive in technical process is improper, although carry out modification, capacity and efficiency lower, do not reach the object of modification, cycle performance and high rate performance are also poor.
The coal-based negative material of embodiment 1 ~ 8 gained has good chemical property: reversible specific capacity >=340.0mAh/g, initial coulomb efficiency >=90%, high rate performance 10C/1C Capacity Ratio >=80.0%, and 1C circulates 500 weeks capability retention >=80.0%.
As can be seen here, the coal-based negative material of lithium ion battery of the present invention highlights advantage on properties, as having height ratio capacity, high rate capability, excellent cycle performance.And method of the present invention adopts the coal of low price to be raw material, prepares cathode material of lithium ion battery, technique is simple, is easy to industrialization.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a coal-based negative material, it is characterized in that, described negative material by coal-based material graphitization internal layer, intermediate layer and be distributed in surface skin form, wherein said intermediate layer is formed by permeating binding agent and coal-based material surface binding agent graphitization in coal-based material hole.
2. coal-based negative material according to claim 1, is characterized in that, described skin is obtained after graphitization by binding agent;
Preferably, the fixed carbon content of described coal-based negative material is>=99.9%, average grain diameter D
50be 2.0 ~ 40.0 μm, specific area is 1.0 ~ 30.0m
2/ g, real density>=2.0g/cc, preferred described average grain diameter D
50be 3.0 ~ 30.0 μm, specific area is 1.0 ~ 20.0m
2/ g, real density>=2.1g/cc;
Preferably, the interlamellar spacing d of 002 crystal face
002for:
degree of disorder I
d/ I
g(area ratio) is 0.1 ~ 0.5, preferably the interlamellar spacing d of described 002 crystal face
002for
degree of disorder I
d/ I
gbe 0.2 ~ 0.4.
3. coal-based negative material according to claim 1 and 2, it is characterized in that, described coal-based negative material is follow-up to its modifying surface, preferably forms the one kind or two or more combination in carbon-coating, inorganic non-metallic simple substance, inorganic non-metallic compound, metal simple-substance, metallic compound on coal-based negative material surface;
Preferably, the modifier of described modification is the one kind or two or more combination in the simple substance of boron, phosphorus, silicon, aluminium or titanium, compound or salt;
Preferably, at least one in coated, mechanical fusion, mechanically modifying, ball milling is modified as described in.
4. the coal-based negative material according to any one of claim 1-3, it is characterized in that, described coal-based material is the one kind or two or more combination in anthracite, coking coal, bottle coal, coal-based coke, or anthracite, coking coal, bottle coal, one kind or two or more and graphite in coal-based coke combination;
Preferably, be 0.1%-95.0% containing the mass percent of graphite in the coal-based material of graphite, be preferably 0.1%-50.0%;
Preferably, described graphite is the one kind or two or more combination in native graphite, Delanium or carbosphere;
Preferably, described native graphite is crystalline flake graphite and/or micro crystal graphite;
Preferably, described binding agent is pitch, resin, high molecular polymer (the one kind or two or more combination in the organic substance such as polyvinyl alcohol, polyacrylonitrile, polyamide, polyacrylic acid, polyacrylamide, polyethylene glycol, poly(ethylene oxide), polymethyl methacrylate, acid anhydrides, coal tar, heavy oil, carbolineum.
5. a preparation method for coal-based negative material described in any one of claim 1-4, comprises and mixing adding binding agent after coal-based material disintegrating; Then described coal-based negative material is namely obtained through die mould, high temperature graphitization;
Preferably, described preparation method comprises and will add binding agent after coal-based material disintegrating and modifier carries out mixing and surface modification treatment; Then described coal-based negative material is namely obtained through die mould, high temperature graphitization.
6. preparation method according to claim 5, is characterized in that, said method comprising the steps of:
(1) by coal-based material disintegrating to average grain diameter D
50=2.0-40.0 μm;
(2) add in step (1) gained material binding agent or, or binding agent and modifier mix, or carry out mixing and modification;
(3), under protective atmosphere or under purification atmosphere, high temperature graphitization process is carried out to step (2) gained material;
Optionally step (3) gained graphitization product carry out sieving and removing magnetic by (4), obtain coal-based negative material;
Preferably, said method comprising the steps of:
(1) by coal-based material disintegrating to average grain diameter D
50=2.0-40.0 μm;
(2) add in step (1) gained material binding agent or, or binding agent and modifier carry out kneading, material is implemented to mixing and the extruding of continous way, material is fully mixed;
(3) material after step (2) kneading is carried out forming processes, obtain the die mould product of cylinder and/or packet;
(4), under protective atmosphere or under purification atmosphere, high temperature graphitization process is carried out to die mould product;
Optionally graphitization product are pulverized by (5), screening, obtain coal-based negative material except magnetic.
7. the preparation method according to claim 5 or 6, is characterized in that, the fixed carbon mass content in described coal-based material is more than 80.0%;
Preferably, described pulverizing be mechanical crushing, air-flow crushing, grind in any a kind;
Preferably, described binding agent accounts for the 0.1%-50.0% of coal-based quality of materials;
Preferably, described modifier accounts for the 0.05%-30.00% of coal-based quality of materials;
Preferably, described graphited equipment adopts any a kind in inner series graphitizing furnace or acheson furnace;
Preferably, described graphited temperature is 2800-3400 DEG C;
Preferably, described forming processes adopts compression molding or isostatic compaction;
Preferably, the equipment of described compression molding adopts any a kind in single column hydraulic machine, four-column hydraulic press, horizontal hydraulic machine, vertical hydraulic press or universal hydraulic machine; The equipment of described isostatic compaction adopts any a kind in screw-type cold isostatic press, frame-type cold isostatic press, hot isostatic press.
Preferably, the bulk density of described die mould product is 1.0 ~ 1.6g/cm
3.
As preferably, described mixing or kneading are solid phase mixing or liquid phase mixing.
8. the preparation method according to claim 5 or 6, it is characterized in that, the equipment of described mixing or kneading is any a kind in high speed dispersor, two stirring two heating kneading machine, vacuum kneading machine, V-Mixer, trough type mixing machine, drum mixer, conical twin-screw mixer, dual cone mixer or solid phase fusion machine;
Preferably, the temperature of described mixing or kneading is 10-300 DEG C;
Preferably, the time of described mixing or kneading is 5-300min;
Preferably, after liquid phase mixing, adopt spray-dired mode to remove solvent, make it fully mix, the temperature of preferably spray drying is 50-350 DEG C.
9. preparation method according to claim 6; it is characterized in that; described protective atmosphere refers to combination one kind or two or more in helium, neon, argon gas, nitrogen or vacuum atmosphere, and purification gas is the one kind or two or more combination of chlorine, freon, fluorine gas.
10. a lithium ion battery, is characterized in that, containing the coal-based negative material that the coal-based negative material described in any one of claim 1-4 or the preparation method described in any one of claim 5-9 obtain in the negative material of described lithium ion battery;
Preferably, the negative material of described lithium ion battery is made up of described active material and cementitious additives.
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Application publication date: 20150603 |