CN103066243A - Coke powder-based cathode material of lithium ion power battery and preparation method thereof - Google Patents
Coke powder-based cathode material of lithium ion power battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a coke powder-based cathode material of a lithium ion power battery and a preparation method thereof. The cathode material has a D50 of 10-30 [mu]m, a minimum granularity of 5 [mu]m, a maximum granularity of 30 [mu]m, and a tap density of 1.1-1.5 g/cm<3>. The cathode material has a core-shell structure, wherein a core is graphitized coke powder, and a shell is composed of coal pitch pyrolytic carbon and metal particles. The cathode material contains 95.00-99.00 % of solid carbon and 1-5 % of metal or metal oxide particles by mass percent. The preparation method comprises crushing, grading and purifying the coke powder, cladding coal pitch on the coke powder particles, graphitizing under a high temperature, attaching metal or metal oxide on the particles, etc. The cathode material is excellent in rate performance, good in high-temperature and low-temperature performances, low in manufacture cost and suitable for large-scale industrialization.
Description
Technical field
The present invention relates to a kind of cathode material for lithium-ion power battery and preparation method thereof, particularly relate to a kind ofly take coal-based coke powder as raw material, have rate cathode material of high power capacity, long-life, low-cost characteristics and preparation method thereof.Belong to the lithium ion battery material preparing technical field.
Background technology
Lithium ion battery is because the excellent properties with aspects such as energy density are large, operating voltage is high, volume is little, quality is light, pollution-free is the desirable energy of development in recent years.Along with popularizing of new-energy automobile, its range of application has been begun to be extended to the fields such as electric motor car by portable type electronic product, and the cost restriction becomes one of key issue of lithium ion battery development.Negative material directly affects the performance of lithium ion battery quality, the reduction of its price affects the reduction of lithium ion battery price, its kind and quality directly determine performance and the price of lithium ion battery, and therefore research cheap, the high-performance negative material is the emphasis of lithium battery industry development always.
Present lithium cell negative pole generally adopts the charcoal negative pole, comprises native graphite, Delanium, carbonaceous mesophase spherules etc.The native graphite good crystallinity, capacity is high, but tap density is low, poor with solvent compatibility, cycle life is not good; Widely used carbonaceous mesophase spherules combination property is good, but manufacturing process is complicated, high expensive, is difficult to satisfy electrokinetic cell to the requirement of cost; Delanium and solvent compatibility are good, but capacity is not high, and during as the power battery cathode material, high rate performance still remains to be improved.In recent years, various raising graphite material capacity and the method for modifying that improves high rate performance have appearred.As in order to improve high rate performance, patent CN102424376A discloses a kind of take coal tar processing heavy product or PETROLEUM PROCESSING heavy product as raw material, through flow processs such as the reformation of Low Temperature Thermal chemistry, middle temperature carbonization, high temperature graphitizations, the artificial plumbago negative pole material high rate performance that makes improves a lot, but reversible capacity is lower slightly, and synthesis cycle is partially long, and cost is higher.In order to improve reversible capacity, patent CN100589264C proposes coal measures or the petroleum-derived heavy oil method by delayed coking-pulverizing-carbonization-catalyzed graphitization-screening, structure organization and the powder characteristics of negative material are improved, thereby increased largely reversible capacity, but its preparation flow is tediously long, need to process and the screening processing through heating for multiple times, this will cause increasing considerably of cost.
In order to reduce the preparation cost of negative material, patent CN102522561A adopts anthracite as raw material, having carried out carbon matrix precursor after with the anthracite high temperature graphitization coats and carbonization treatment, first efficient and cycle performance have been improved, but preparation flow is still partially long, and product belongs to the character of micro crystal graphite, and high rate performance is not good.Patent CN102351163A has proposed to make nano-sized carbon microballoon negative material by asphaltic base or the amphipathic Carbon Materials of petroleum coke base through the step that obtain solution, stirring and rectifying separate, this negative material has the advantage of capacity height, good rate capability, and preparation technology is simple, flow process is short, but because raw material has only passed through middle temperature carbonization treatment, the products therefrom degree of graphitization is not high, particle diameter is too small and specific area is excessive, so that inefficiency first.
Summary of the invention
The object of the invention is to overcome the problem that prior art exists, a kind of good cycle is provided, capacity is high, the negative material reversible capacity height that the lithium-ion-power cell that price is low uses coke powder base negative material and technological process is short, preparation cost is low, prepare, good rate capability, life-span long lithium-ion-power cell coke powder base cathode material preparation method.
A kind of lithium-ion-power cell of the present invention coke powder base negative material, described carbon comprises pure coal-based coke powder, coal tar pitch RESEARCH OF PYROCARBON, described negative material has nucleocapsid structure, its core is the pure coal-based coke powder after graphitization processing, and shell consists of by the coal tar pitch RESEARCH OF PYROCARBON after graphitization processing and at the shell surface chemical metal plating.
A kind of lithium-ion-power cell of the present invention coke powder base negative material, described carbon by coal tar pitch and pure coke powder in mass ratio 1:10 ~ 1:2 form, the mass fraction fixed carbon content of carbon in described negative material is 95.00 ~ 99.00%, and the mass fraction that surface chemical metal plating accounts for described negative material is 1 ~ 5%.
A kind of lithium-ion-power cell of the present invention is with coke powder base negative material, and described negative material mean particle size D 50 is 10 ~ 30um, and minimum particle size is more than or equal to 5um, and maximum particle size is less than or equal to 30um, tap density 1.1 ~ 1.5g/cm
3
A kind of lithium-ion-power cell of the present invention preparation method of coke powder base negative material may further comprise the steps:
The first step: the coal-based coke powder of raw material is dry, broken, classification
The coal-based coke powder of raw material is carried out drying, fragmentation and classification;
Second step: coal-based coke powder removal of impurities
The coal-based coke powder of first step gained mixed with acid solution sizes mixing, the control reaction condition, make silicon dioxide, iron oxide, aluminium oxide impurity and the acid reaction in the coke powder after, the washing drying obtains high-purity coal-based coke powder;
The 3rd step: high-purity coal-based coke powder surface coats coal tar pitch
The high-purity coal-based coke powder of second step gained is immersed in the coal tar pitch solution, and stirring obtains mixed solution, and the solvent of mixed solution is removed in evaporation below 100 ℃, obtains take high-purity coal-based coke powder as nuclear, coal tar pitch is the nucleocapsid structure of shell;
The 4th step: nucleocapsid structure graphitization processing
The compound that adds boron or boron in the 3rd step gained nucleocapsid structure is heated to 2200-2800 ℃ of insulation 10min-2h as catalyst in inert atmosphere, carry out graphitization processing;
The 5th step: surface chemical plating
With the nucleocapsid structure surface chemical metal plating of the 4th step gained through graphitization processing.
A kind of lithium-ion-power cell of the present invention preparation method of coke powder base negative material, in the first step, described coal-based coke powder is carried out drying, fragmentation and classification, be with the coal-based coke powder of raw material behind 120 ~ 150 ℃ of dry 24h, carry out fragmentation and classification at the airflow crash classifying equipoment again,, obtain mean particle size D 50 and be 10 ~ 30um, minimum particle size more than or equal to 5um and the maximum particle size coal-based coke powder less than or equal to 30um.
A kind of lithium-ion-power cell of the present invention preparation method of coke powder base negative material, in the second step, described acid solution is selected from one or several in hydrofluoric acid, hydrochloric acid, sulfuric acid, the salpeter solution, and the acid solution mass percentage concentration is 15-35%; Reaction condition is: temperature 20-60 ℃, and time 1-10h; Mixing the liquid-solid mass ratio of sizing mixing is 2:1 ~ 10:1.
A kind of lithium-ion-power cell of the present invention is with the preparation method of coke powder base negative material, acid solution by at least a acid in hydrofluoric acid and hydrochloric acid, sulfuric acid, the nitric acid in mass ratio 1:1 ~ 5:1 mix formation.
A kind of lithium-ion-power cell of the present invention is with the preparation method of coke powder base negative material, and in the 3rd step, described coal tar pitch solution is saturated solution, and solvent is selected from least a in toluene, kerosene, pyridine, acetone, the carbon disulfide; The liquid-solid ratio of described mixed solution is that the amount of 1:10 ~ 1:2 is determined by the mass ratio of coal tar pitch and purifying coke powder; Described mixed solution is 60 ~ 80 ℃ of lower evaporation desolventizings, the purifying coke powder nucleocapsid structure that obtain take high-purity coal-based coke powder as nuclear, coal tar pitch coats as the coal tar pitch of shell.
A kind of lithium-ion-power cell of the present invention preparation method of coke powder base negative material, in the 4th step, the compound of described boron or boron is selected from least a in boron simple substance, boron oxide, boron nitride, boron carbide, boric acid, the borate, and the addition of the compound of boron or boron accounts for the 0-10% of high-purity coal-based coke powder mass percent in the nucleocapsid structure; Described inert atmosphere is the nitrogen of nitrogen, argon gas or arbitrary proportion and the mist of argon gas.
A kind of lithium-ion-power cell of the present invention preparation method of coke powder base negative material, the addition of the compound of boron or boron accounts for the 0.5-5% of high-purity coal-based coke powder mass percent in the nucleocapsid structure; Described inert atmosphere is argon gas atmosphere.
A kind of lithium-ion-power cell of the present invention is with the preparation method of coke powder base negative material, and in the 5th step, metal is selected from a kind of among Ag, Cu, the Ni, and metal quality is 1 ~ 5% of negative material gross mass.
The present invention adopts said components proportioning and process, take coal-based coke powder as raw material, the preparation lithium cell cathode material, technological process is short, preparation cost is low, the product that obtains is owing to adopted nucleocapsid structure, formed uniform and stable bitumencarb coating layer at coal-based coke powder foundation stone China ink particle surface, in the high reversible capacity that keeps coal-based coke powder foundation stone China ink, effectively improved material structure, the structure that stops the common embedding of electrolyte and cause is caved in, and therefore has reversible capacity height, good rate capability, long characteristics of life-span.Coal-based coke powder be metallurgical and chemical industry in coke production with utilize the byproduct that produces in the process, general being used as back joined coking or fuel, added value is lower.The present invention is based on coal-based coke powder is the soft carbon structure with certain degree of graphitization, proposes the lithium ion battery negative material that preparation has high added value take coal-based coke powder as raw material.Solve on the one hand the recycling problem of the coal-based coke powder of a large amount of low values, can obtain low cost, high performance lithium ionic cell cathode material on the other hand, satisfied the growing market demand, will bring very large economic benefit and social benefit.
The advantage that the present invention compared with prior art has is: adopt the cheap coal-based coke powder of coke by-products as raw material, utilize the characteristics that itself have certain degree of graphitization, through processing steps such as purification, coating, heat treatment, surface modifications, obtained being applicable to the Delanium of lithium ion battery negative, have discharge capacity height, good cycle, advantage that preparation cost is low, and technique is simple, is easy to suitability for industrialized production.
Description of drawings
Accompanying drawing 1 is the stereoscan photograph of embodiment 1 prepared negative material.
Accompanying drawing 2 is the XRD collection of illustrative plates of embodiment 1 prepared negative material.
Accompanying drawing 3 is the first charge-discharge curve chart of embodiment 1 prepared negative material.
Can find out from accompanying drawing 1: the embodiment of the invention 1 prepared negative material has typical graphite flake layer structure, and average grain diameter D50 is 22um, and particle size distribution is between 5-30um, and particle size distribution range is narrow.
Can find out from accompanying drawing 2: three diffraction maximums (002,100,004) that significantly characterize the graphite charcoal have appearred in the XRD collection of illustrative plates of the embodiment of the invention 1 prepared negative material, have shown the crystallinity that material is good.
Can find out from accompanying drawing 3: the first charge-discharge platform of the embodiment of the invention 1 prepared negative material is long, and reversible capacity reaches 356.4mAh/g first and mild, and coulombic efficiency is 92.3% first, characterizes out good chemical property.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail, but the present invention is not limited to following examples.
Embodiment 1:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after the graphitization, shell consists of by the coal tar pitch RESEARCH OF PYROCARBON and at shell surface chemical metal plating Ag, negative material fixed carbon content 99.00%, the mass fraction of metal A g is that 1%, D50 is 22um, minimum particle size 5um, maximum particle size 30um, tap density is 1.1g/cm
3
Prepare the lithium-ion-power cell preparation method of coke powder base negative material take coal-based coke powder as raw material, may further comprise the steps:
(1) with average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, then 120 ℃ of lower dry 24h are ground into average grain diameter 20 μ m with the eddy airstream pulverizer with it in blast furnace, and classification goes out the particle of particle size range 5-30 μ m.
The material mass concentration that (2) will meet particle size range is that 19% hydrofluoric acid solution leaches, the control reaction condition is that liquid-solid mass ratio is 3:1, and reaction temperature is 25 ℃, and the processing time is 1h, reacted coke powder is dry through washing to the neutrality, and the purifying coke powder purity that obtains is 99.6%.
(3) coat coal tar pitch on high-purity coal-based coke powder surface, at first the 100g coal tar pitch is dissolved in and forms coating solution in the 500mL toluene; Then 1000g purifying coke powder is joined in the coating solution, mechanical agitation evenly namely makes mixed solution; At 60 ℃ of lower evaporation mixed solutions, remove toluene solvant at last, obtain the purifying coke powder that coal tar pitch coats.
(4) take by weighing the purifying coke powder 500g that coal tar pitch coats, add boron oxide 10g, after mixing, be positioned in the superhigh temperature graphitizing furnace, under 2800 ℃, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after the graphitization processing.
(5) enclose metal A g on the clad material surface, first with clad material at SnCl
2Sensitization 1 ~ 2min after heat water rinse in the solution, after then will drying and the clad material of cooling (it is as follows that chemistry crosses the liquid collocation method: first with 2gAgNO in the chemical plating fluid for preparing than being added to by 1% loading
3Be dissolved in 60mI H
2Among the O, and in situation about constantly stirring, add ammoniacal liquor, until the Ag that separates out
2The fully dissolving of O precipitation, then add again blackening of solution behind the NaOH of 2.5g/100mI, it is fully limpid to solution to continue to drip ammoniacal liquor, be made into A liquid, in addition 45g glucose and 4g tartaric acid are dissolved in the 1L water, boil 10min, add 100mI ethanol after the cooling, be made into B liquid, namely get the chemical liquid that crosses by 1:1 mixing A, B two liquid.), in 30 ℃ water bath with thermostatic control, behind the stirring reaction 1h, with this suspension filtered, be washed to neutrality, place 170 ℃ the dry 12h of vacuum drying chamber after, obtain lithium-ion-power cell with coke powder base negative material.Fig. 1 is the stereoscan photograph of coke powder base negative material, and Fig. 2 is the XRD collection of illustrative plates of coke powder base negative material.
Detect: with gained coke powder base negative material, conductive acetylene is black and binding agent PVDF is mixed and made into electrode slice with mass percent 85:5:5, and form the electrochemistry embedding of half-cell test material/take off the lithium performance with metal lithium sheet, electrolyte is commercially available 1M LiPF
6/ EC+DMC solution.Utilize the Land battery test system that above-mentioned half-cell is at room temperature carried out the constant current charge-discharge performance test, charge-discharge magnification is 0.2C(74mA/g) and 1C(372mA/g), the charging/discharging voltage scope is 0.01-2V.Fig. 3 is the charging and discharging curve of the prepared artificial plumbago negative pole material of present embodiment, and the various performance parameters of negative material sees Table 1.
Embodiment 2:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after the graphitization, shell consists of by the coal tar pitch RESEARCH OF PYROCARBON and at shell surface chemical metal plating Cu, negative material fixed carbon content 98.00%, the mass fraction of metal Cu is that 2%, D50 is 17um, minimum particle size 5um, maximum particle size 30um, tap density is 1.18g/cm
3
Prepare the lithium-ion-power cell preparation method of coke powder base negative material take coal-based coke powder as raw material, may further comprise the steps:
(1) with average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, then 130 ℃ of lower dry 24h are ground into average grain diameter 15 μ m with the eddy airstream pulverizer with it in blast furnace, and classification goes out the particle of particle size range 5-30 μ m.
The material mass concentration that (2) will meet particle size range is that 19% hydrofluoric acid solution leaches, the control reaction condition is that liquid-solid mass ratio is 3:1, and reaction temperature is 25 ℃, and the processing time is 1h, reacted coke powder is dry through washing to the neutrality, and the purifying coke powder purity that obtains is 99.7%.
(3) coat coal tar pitch on high-purity coal-based coke powder surface, at first the 100g coal tar pitch is dissolved in and forms coating solution in the 400mL kerosene; Then 1000g purifying coke powder is joined in the coating solution, mechanical agitation evenly namely makes mixed solution; At 80 ℃ of lower evaporation mixed solutions, remove kerosene solvent at last, obtain the purifying coke powder that coal tar pitch coats.
(4) take by weighing the purifying coke powder 500g that coal tar pitch coats, add boron oxide 10g, after mixing, be positioned in the superhigh temperature graphitizing furnace, under 2800 ℃, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after the graphitization processing.
(5) enclose metal Cu particle on the clad material surface, first with the SnCl of clad material at 100g/L
2Sensitization 1 ~ 2min after heat water rinse in the solution, after then will drying and the clad material of cooling (it is composed as follows that chemistry crosses liquid: CuSO in the chemical plating fluid for preparing than being added to by 2% loading
45HO
215g/L, CH
2O (37%) 12mL/L, Na
2EDTA30g/L, (C
5H
4N)
20.1g/L NaOH transfers pH to 12 ~ 13), in 30 ℃ water bath with thermostatic control, behind the stirring reaction 1h, with this suspension filtered, be washed to neutrality, put in 380 ℃ of hydrogen atmospheres and be incubated 5h, after the stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result sees Table 1.
Embodiment 3:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after the graphitization, shell consists of by the coal tar pitch RESEARCH OF PYROCARBON and at shell surface chemical metal plating Ni, negative material fixed carbon content 96.00%, the mass fraction of metal Ni particle is that 4%, D50 is 22um, minimum particle size 5um, maximum particle size 30um, tap density is 1.1g/cm
3
Prepare the lithium-ion-power cell preparation method of coke powder base negative material take coal-based coke powder as raw material, may further comprise the steps:
(1) with average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, then 140 ℃ of lower dry 12h are ground into average grain diameter 20 μ m with the eddy airstream pulverizer with it in blast furnace, and classification goes out the particle of particle size range 5-30 μ m.
The material mass concentration that (2) will meet particle size range is that 30% hydrofluoric acid and hydrochloric acid mixed solution leach, hydrofluoric acid and hydrochloric acid mass ratio are 1:1, the control reaction condition is that liquid-solid mass ratio is 5:1, reaction temperature is 35 ℃, processing time is 2h, reacted coke powder is dry through washing to the neutrality, and the purifying coke powder purity that obtains is 99.8%.
(3) coat coal tar pitch on high-purity coal-based coke powder surface, at first the 100g coal tar pitch is dissolved in and forms coating solution in the 600mL acetone; Then 1000g purifying coke powder is joined in the coating solution, mechanical agitation evenly namely makes mixed solution; At 70 ℃ of lower evaporation mixed solutions, remove acetone solvent at last, obtain the purifying coke powder that coal tar pitch coats.
(4) take by weighing the purifying coke powder 500g that coal tar pitch coats, add boron oxide 10g, after mixing, be positioned in the superhigh temperature graphitizing furnace, under 2800 ℃, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after the graphitization processing.
(5) enclose metal Ni particle on the clad material surface, first with the SnCl of clad material at 100g/L
2Sensitization 1 ~ 2min after heat water rinse in the solution, after then will drying and the clad material of cooling (it is composed as follows that chemistry crosses liquid: NiCl in the chemical plating fluid for preparing than being added to by 4% loading
26H
2O30g/L, NH
4Cl50g/L, natrium citricum 85g/L, inferior sodium phosphate 15g/L, ammoniacal liquor is transferred pH to 8.5 ~ 9), in 90 ℃ water bath with thermostatic control behind the stirring reaction 1h, with this suspension filtered, be washed to neutrality, place 380 ℃ of hydrogen atmospheres to be incubated 5h, after the stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result sees Table 1.
Embodiment 4:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after the graphitization, shell consists of by the coal tar pitch RESEARCH OF PYROCARBON and at shell surface chemical metal plating Ni, negative material fixed carbon content 95.00%, the mass fraction of metal Ni particle is that 5%, D50 is 27um, minimum particle size 5um, maximum particle size 30um, tap density is 1.15g/cm
3
Prepare the lithium-ion-power cell preparation method of coke powder base negative material take coal-based coke powder as raw material, may further comprise the steps:
(1) with average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, then 140 ℃ of lower dry 24h are ground into average grain diameter 25 μ m with the eddy airstream pulverizer with it in blast furnace, and classification goes out the particle of particle size range 5-30 μ m.
The material mass concentration that (2) will meet particle size range is that 30% hydrofluoric acid and sulfuric acid mixed solution leach, hydrofluoric acid and sulfuric acid mass ratio are 1:1, the control reaction condition is that liquid-solid mass ratio is 3:1, reaction temperature is 25 ℃, processing time is 1h, reacted coke powder is dry through washing to the neutrality, and the purifying coke powder purity that obtains is 99.7%.
(3) coat coal tar pitch on high-purity coal-based coke powder surface, at first the 100g coal tar pitch is dissolved in and forms coating solution in the 500mL toluene; Then 1000g purifying coke powder is joined in the coating solution, mechanical agitation evenly namely makes mixed solution; At 70 ℃ of lower evaporation mixed solutions, remove toluene solvant at last, obtain the purifying coke powder that coal tar pitch coats.
(4) take by weighing the purifying coke powder 500g that coal tar pitch coats, add boron oxide 10g, after mixing, be positioned in the superhigh temperature graphitizing furnace, under 2800 ℃, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after the graphitization processing.
(5) enclose metal Ni particle on the clad material surface, first with the SnCl of clad material at 100g/L
2Sensitization 1 ~ 2min after heat water rinse in the solution, after then will drying and the clad material of cooling (it is composed as follows that chemistry crosses liquid: NiCl in the chemical plating fluid for preparing than being added to by 5% loading
26H
2O30g/L, NH
4Cl50g/L, natrium citricum 85g/L, inferior sodium phosphate 15g/L, ammoniacal liquor is transferred pH to 8.5 ~ 9), in 90 ℃ water bath with thermostatic control behind the stirring reaction 1h, with this suspension filtered, be washed to neutrality, place 380 ℃ of hydrogen atmospheres to be incubated 5h, after the stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result sees Table 1.
Embodiment 5:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after the graphitization, shell consists of by the coal tar pitch RESEARCH OF PYROCARBON and at shell surface chemical metal plating Cu, negative material fixed carbon content 97.00%, the mass fraction of metal Cu particle is that 3%, D50 is 17um, minimum particle size 5um, maximum particle size 30um, tap density is 1.18g/cm
3
Prepare the lithium-ion-power cell preparation method of coke powder base negative material take coal-based coke powder as raw material, may further comprise the steps:
(1) with average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, then 130 ℃ of lower dry 24h are ground into average grain diameter 15 μ m with the eddy airstream pulverizer with it in blast furnace, and classification goes out the particle of particle size range 5-30 μ m.
The material mass concentration that (2) will meet particle size range is that 30% hydrofluoric acid and hydrochloric acid mixed solution leach, hydrofluoric acid and hydrochloric acid mass ratio are 1:1, the control reaction condition is that liquid-solid mass ratio is 4:1, reaction temperature is 40 ℃, processing time is 2h, reacted coke powder is dry through washing to the neutrality, and the purifying coke powder purity that obtains is 99.9%.
(3) coat coal tar pitch on high-purity coal-based coke powder surface, at first the 100g coal tar pitch is dissolved in and forms coating solution in the 400mL kerosene; Then 1000g purifying coke powder is joined in the coating solution, mechanical agitation evenly namely makes mixed solution; At 80 ℃ of lower evaporation mixed solutions, remove kerosene solvent at last, obtain the purifying coke powder that coal tar pitch coats.
(4) take by weighing the purifying coke powder 500g that coal tar pitch coats, add boron oxide 20g, after mixing, be positioned in the superhigh temperature graphitizing furnace, under 2800 ℃, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after the graphitization processing.
(5) enclose metal Cu particle on the clad material surface, first with clad material sensitization 1 ~ 2min after heat water rinse in the SnCl2 of 100g/L solution, after then will drying and the clad material of cooling (it is composed as follows that chemistry crosses liquid: CuSO in the chemical plating fluid for preparing than being added to by 3% loading
45HO
215g/L, CH
2O (37%) 12mL/L, Na
2EDTA30g/L, (C
5H
4N)
20.1g/L NaOH transfers pH to 12 ~ 13), in 30 ℃ water bath with thermostatic control, behind the stirring reaction 1h, with this suspension filtered, be washed to neutrality, put in 380 ℃ of hydrogen atmospheres and be incubated 5h, after the stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result sees Table 1.
Embodiment 6:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after the graphitization, shell consists of by the coal tar pitch RESEARCH OF PYROCARBON and at shell surface chemical metal plating Ni, negative material fixed carbon content 96.00%, the mass fraction of metal Ni particle is that 4%, D50 is 22um, minimum particle size 5um, maximum particle size 30um, tap density is 1.1g/cm3.
Prepare the lithium-ion-power cell preparation method of coke powder base negative material take coal-based coke powder as raw material, may further comprise the steps:
(1) with average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, then 140 ℃ of lower dry 12h are ground into average grain diameter 20 μ m with the eddy airstream pulverizer with it in blast furnace, and classification goes out the particle of particle size range 5-30 μ m.
The material mass concentration that (2) will meet particle size range is that 30% hydrofluoric acid and hydrochloric acid mixed solution leach, hydrofluoric acid and hydrochloric acid mass ratio are 2:1, the control reaction condition is that liquid-solid mass ratio is 4:1, reaction temperature is 40 ℃, processing time is 2h, reacted coke powder is dry through washing to the neutrality, and the purifying coke powder purity that obtains is 99.9%.
(3) coat coal tar pitch on high-purity coal-based coke powder surface, at first the 100g coal tar pitch is dissolved in and forms coating solution in the 600mL acetone; Then 1000g purifying coke powder is joined in the coating solution, mechanical agitation evenly namely makes mixed solution; At 70 ℃ of lower evaporation mixed solutions, remove acetone solvent at last, obtain the purifying coke powder that coal tar pitch coats.
(4) take by weighing the purifying coke powder 500g that coal tar pitch coats, add boron oxide 20g, after mixing, be positioned in the superhigh temperature graphitizing furnace, under 2600 ℃, carry out graphitization processing, temperature retention time 50min, naturally cool to room temperature, obtain the clad material after the graphitization processing.
(5) enclose metal Ni particle on the clad material surface, first with the SnCl of clad material at 100g/L
2Sensitization 1 ~ 2min after heat water rinse in the solution, after then will drying and the clad material of cooling (it is composed as follows that chemistry crosses liquid: NiCl in the chemical plating fluid for preparing than being added to by 4% loading
26H
2O30g/L, NH
4Cl50g/L, natrium citricum 85g/L, inferior sodium phosphate 15g/L, ammoniacal liquor is transferred pH to 8.5 ~ 9), in 90 ℃ water bath with thermostatic control behind the stirring reaction 1h, with this suspension filtered, be washed to neutrality, place 380 ℃ of hydrogen atmospheres to be incubated 5h, after the stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result sees Table 1.
Comparative Examples 1:
With average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, then 105 ℃ of lower dry 12h are ground into average grain diameter 20 μ m with the eddy airstream pulverizer with it in blast furnace.Be that 30% hydrofluoric acid and hydrochloric acid mixed solution leach with the material mass concentration, hydrofluoric acid and hydrochloric acid mass ratio are 1:1, the control reaction condition is that liquid-solid mass ratio is 4:1, reaction temperature is 40 ℃, processing time is 2h, reacted coke powder is dry through washing to the neutrality, and the purifying coke powder purity that obtains is 99.8%.Take by weighing purifying coke powder 500g, add boron oxide 10g, after mixing, be positioned in the superhigh temperature graphitizing furnace, carry out graphitization processing under 2800 ℃, temperature retention time 20min naturally cools to room temperature, obtains man-made graphite cathode material for lithium ion battery.Detect: with embodiment 1.Test result sees Table 1.
Comparative Examples 2:
With average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, then 105 ℃ of lower dry 12h are ground into average grain diameter 20 μ m with the eddy airstream pulverizer with it in blast furnace, and classification goes out the particle of particle size range 5-30 μ m.The material mass concentration that will meet particle size range is that 30% hydrofluoric acid and hydrochloric acid mixed solution leach, hydrofluoric acid and hydrochloric acid mass ratio are 1:1, the control reaction condition is that liquid-solid mass ratio is 4:1, reaction temperature is 40 ℃, processing time is 2h, reacted coke powder is dry through washing to the neutrality, and the purifying coke powder purity that obtains is 99.8%.Take by weighing purifying coke powder 500g, be positioned in the superhigh temperature graphitizing furnace, carry out graphitization processing under 2800 ℃, temperature retention time 20min naturally cools to room temperature, obtains man-made graphite cathode material for lithium ion battery.Detect: with embodiment 1.Test result sees Table 1.
Table 1
As can be seen from Table 1, when the coke powder foundation stone ink material of the present invention's preparation was used for lithium-ion-power cell, discharge capacity was high first, enclosed pasture efficient is good first; undamped after the little multiplying power circulation 100 times, high rate during charging-discharging is good, shows good high rate performance and cyclical stability.
Claims (11)
1. a lithium-ion-power cell is with coke powder base negative material, consisted of by carbon and metal, described carbon comprises pure coal-based coke powder, coal tar pitch RESEARCH OF PYROCARBON, it is characterized in that: described negative material has nucleocapsid structure, its core is the pure coal-based coke powder after graphitization processing, and shell consists of by the coal tar pitch RESEARCH OF PYROCARBON after graphitization processing and at the shell surface chemical metal plating.
According to claim 1 described a kind of lithium-ion-power cell with coke powder base negative material, it is characterized in that: described carbon by coal tar pitch and pure coke powder in mass ratio 1:10 ~ 1:2 form, the mass fraction of carbon in described negative material is 95.00 ~ 99.00%, and the mass fraction that surface chemical metal plating accounts for described negative material is 1 ~ 5%.
According to claim 1 described a kind of lithium-ion-power cell with coke powder base negative material, it is characterized in that: described negative material mean particle size D 50 is 10 ~ 30um, minimum particle size is more than or equal to 5um, and maximum particle size is less than or equal to 30um, tap density 1.1 ~ 1.5g/cm
3
4. the described a kind of lithium-ion-power cell of any one may further comprise the steps with the preparation method of coke powder base negative material according to claim 1-3:
The first step: the coal-based coke powder of raw material is dry, broken, classification
The coal-based coke powder of raw material is carried out drying, fragmentation and classification;
Second step: coal-based coke powder removal of impurities
The coal-based coke powder of first step gained mixed with acid solution sizes mixing, the control reaction condition, make silicon dioxide, iron oxide, aluminium oxide impurity and the acid reaction in the coke powder after, the washing drying obtains pure coal-based coke powder;
The 3rd step: high-purity coal-based coke powder surface coats coal tar pitch
The pure coal-based coke powder of second step gained is immersed in the coal tar pitch solution, and stirring obtains mixed solution, and the solvent of mixed solution is removed in evaporation below 100 ℃, obtains take high-purity coal-based coke powder as nuclear, coal tar pitch is the nucleocapsid structure of shell;
The 4th step: nucleocapsid structure graphitization processing
The compound that adds boron or boron in the 3rd step gained nucleocapsid structure is heated to 2200-2800 ℃ of insulation 10min-2h as catalyst in inert atmosphere, carry out graphitization processing;
The 5th step: surface chemical plating
With the nucleocapsid structure surface chemical metal plating of the 4th step gained through graphitization processing.
According to claim 4 described a kind of lithium-ion-power cell with the preparation method of coke powder base negative material, it is characterized in that: in the first step, described coal-based coke powder is carried out drying, fragmentation and classification, be with the coal-based coke powder of raw material behind 120 ~ 150 ℃ of dry 24h, carry out fragmentation and classification at the airflow crash classifying equipoment again,, obtain mean particle size D 50 and be 10 ~ 30um, minimum particle size more than or equal to 5um and the maximum particle size coal-based coke powder less than or equal to 30um.
According to claim 4 described a kind of lithium-ion-power cell with the preparation method of coke powder base negative material, it is characterized in that: in the second step, described acid solution is selected from one or several in hydrofluoric acid, hydrochloric acid, sulfuric acid, the salpeter solution, and the acid solution mass percentage concentration is 15-35%; Reaction condition is: temperature 20-60 ℃, and time 1-10h; Mixing the liquid-solid mass ratio of sizing mixing is 2:1 ~ 10:1.
7. described a kind of lithium-ion-power cell is characterized in that with the preparation method of coke powder base negative material according to claim 6: acid solution by at least a acid in hydrofluoric acid and hydrochloric acid, sulfuric acid, the nitric acid in mass ratio 1:1 ~ 5:1 mix formation.
According to claim 4 described a kind of lithium-ion-power cell with the preparation method of coke powder base negative material, it is characterized in that: in the 3rd step, described coal tar pitch solution is saturated solution, and solvent is selected from least a in toluene, kerosene, pyridine, acetone, the carbon disulfide; The liquid-solid ratio of described mixed solution is that the amount of 1:10 ~ 1:2 is determined by the mass ratio of coal tar pitch and purifying coke powder; Described mixed solution is 60 ~ 80 ℃ of lower evaporation desolventizings, the purifying coke powder nucleocapsid structure that obtain take high-purity coal-based coke powder as nuclear, coal tar pitch coats as the coal tar pitch of shell.
According to claim 4 described a kind of lithium-ion-power cell with the preparation method of coke powder base negative material, it is characterized in that: in the 4th step, the compound of described boron or boron is selected from least a in boron simple substance, boron oxide, boron nitride, boron carbide, boric acid, the borate, and the addition of the compound of boron or boron accounts for the 0-10% of high-purity coal-based coke powder mass percent in the nucleocapsid structure; Described inert atmosphere is the nitrogen of nitrogen, argon gas or arbitrary proportion and the mist of argon gas.
10. described a kind of lithium-ion-power cell is with the preparation method of coke powder base negative material according to claim 9, and it is characterized in that: the addition of the compound of boron or boron accounts for the 0.5-5% of high-purity coal-based coke powder mass percent in the nucleocapsid structure; Described inert atmosphere is argon gas atmosphere.
11. according to claim 4 described a kind of lithium-ion-power cell preparation of coke powder base negative material
Method is characterized in that: in the 5th step, metal is selected from a kind of among Ag, Cu, the Ni, and metal quality is 1 ~ 5% of negative material gross mass.
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