CN103066243B - 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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- CN103066243B CN103066243B CN201210519465.9A CN201210519465A CN103066243B CN 103066243 B CN103066243 B CN 103066243B CN 201210519465 A CN201210519465 A CN 201210519465A CN 103066243 B CN103066243 B CN 103066243B
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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 of with coal-based coke powder for raw material, there is the rate cathode material and preparation method thereof of high power capacity, long-life, low cost feature.Belong to lithium ion battery material preparing technical field.
Background technology
Lithium ion battery, owing to having the excellent properties of the aspects such as energy density is 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 is extended to the fields such as electric motor car by portable type electronic product, and cost restriction becomes one of key issue of lithium ion battery development.Negative material directly affects 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 that is cheap, high-performance negative material is the emphasis of lithium battery industry development always.
Current lithium cell negative pole generally adopts charcoal negative pole, comprises native graphite, Delanium, carbonaceous mesophase spherules etc.Native graphite good crystallinity, capacity is high, but tap density is low, with solvent compatibility is poor, cycle life is not good; Widely used carbonaceous mesophase spherules combination property is good, but manufacturing process is complicated, high expensive, is difficult to meet the requirement of electrokinetic cell to cost; Delanium and solvent compatibility good, but capacity is not high, and during as power battery cathode material, high rate performance still has much room for improvement.In recent years, various raising graphite material capacity and the method for modifying improving high rate performance have been there is.As in order to improve high rate performance, patent CN102424376A disclose a kind of with coal tar processing heavy product or PETROLEUM PROCESSING heavy product for raw material, through flow processs such as Low Temperature Thermal chemistry reformation, middle temperature carbonization, high temperature graphitizations, obtained artificial plumbago negative pole material high rate performance improves a lot, but reversible capacity is lower slightly, and synthesis cycle is partially long, cost is higher.In order to improve reversible capacity, patent CN100589264C proposes method coal measures or petroleum-derived heavy oil being passed through delayed coking-pulverizing-carbonization-catalyzed graphitization-screening, the structure organization of negative material and powder characteristics are improved, thus increase reversible capacity largely, but its preparation flow is tediously long, need through heating for multiple times process and screening process, this will cause increasing considerably of cost.
In order to reduce the preparation cost of negative material, patent CN102522561A adopts anthracite as raw material, carry out the coated and carbonization treatment of carbon matrix precursor after by anthracite high temperature graphitization, improve efficiency and cycle performance first, but preparation flow is still partially long, and product belongs to the character of micro crystal graphite, high rate performance is not good.Patent CN102351163A proposes the step be separated through obtain solution, stirring and rectifying by asphaltic base or the amphipathic Carbon Materials of petroleum coke base and obtains nano-sized carbon microballoon negative material, this negative material has that capacity is high, the advantage of good rate capability, and preparation technology is simple, flow process is short, but because raw material only have passed through middle temperature carbonization treatment, products therefrom degree of graphitization is not high, particle diameter is too small and specific area is excessive, makes inefficiency first.
Summary of the invention
The object of the invention is to overcome prior art Problems existing, a kind of good cycle is provided, capacity is high, the lithium-ion-power cell coke powder base negative material that price is low and the lithium-ion-power cell coke powder base cathode material preparation method that technological process is short, preparation cost is low, high, the good rate capability of negative material reversible capacity of preparation, life-span are long.
A kind of lithium-ion-power cell coke powder base negative material of the present invention, 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 is by the coal tar pitch RESEARCH OF PYROCARBON after graphitization processing and form at shell layer surface chemical plating metal.
A kind of lithium-ion-power cell coke powder base negative material of the present invention, 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 coke powder base negative material of the present invention, 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.
The preparation method of a kind of lithium-ion-power cell coke powder of the present invention base negative material, comprises the following steps:
The first step: the coal-based coke powder of raw material is dry, broken, classification
Coal-based for raw material coke powder is carried out drying, fragmentation and classification;
Second step: coal-based coke powder removal of impurities
Mixed with acid solution by coal-based for first step gained coke powder and size mixing, control reaction condition, after making the silicon dioxide in coke powder, iron oxide, alumina impurities and acid reaction, washing is dry, obtains high-purity coal-based coke powder;
3rd step: high-purity coal-based coke powder Surface coating coal tar pitch
High-purity for second step gained coal-based coke powder is immersed in coal tar pitch solution, stirs and obtain mixed solution, the solvent of less than 100 DEG C evaporation removing mixed solutions, obtain with high-purity coal-based coke powder be core, the coal tar pitch nucleocapsid structure that is shell;
4th step: nucleocapsid structure graphitization processing
In the 3rd step gained nucleocapsid structure, add the compound of boron or boron as catalyst, be heated to 2200-2800 DEG C of insulation 10min-2h in an inert atmosphere, carry out graphitization processing;
5th step: surface chemical plating
By the nucleocapsid structure surface chemical metal plating of the 4th step gained through graphitization processing.
The preparation method of a kind of lithium-ion-power cell coke powder of the present invention base negative material, in the first step, described carries out drying, fragmentation and classification to coal-based coke powder, be by coal-based for raw material coke powder after 120 ~ 150 DEG C of dry 24h, fragmentation and classification is carried out again on airflow crash classifying equipoment,, obtain that 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 the coal-based coke powder of 30um.
The preparation method of a kind of lithium-ion-power cell coke powder of the present invention base negative material, in second step, described acid solution be selected from hydrofluoric acid, hydrochloric acid, sulfuric acid, salpeter solution one or several, acid solution mass percentage concentration is 15-35%; Reaction condition is: temperature 20-60 DEG C, time 1-10h; Mixing the liquid-solid mass ratio of sizing mixing is 2:1 ~ 10:1.
The preparation method of a kind of lithium-ion-power cell coke powder of the present invention base negative material, acid solution by hydrofluoric acid and at least one acid in hydrochloric acid, sulfuric acid, nitric acid in mass ratio 1:1 ~ 5:1 mix and form.
The preparation method of a kind of lithium-ion-power cell coke powder of the present invention base negative material, in the 3rd step, described coal tar pitch solution is saturated solution, and solvent is selected from least one in toluene, kerosene, pyridine, acetone, carbon disulfide; The amount that the liquid-solid ratio of described mixed solution is 1:10 ~ 1:2 by the mass ratio of coal tar pitch and purifying coke powder is determined; Described mixed solution is evaporation of solvent at 60 ~ 80 DEG C, obtain with high-purity coal-based coke powder be core, the coated purifying coke powder nucleocapsid structure of the coal tar pitch coal tar pitch that is shell.
The preparation method of a kind of lithium-ion-power cell coke powder of the present invention base negative material, in 4th step, the compound of described boron or boron is selected from least one in boron simple substance, boron oxide, boron nitride, boron carbide, boric acid, 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 nucleocapsid structure; Described inert atmosphere is the nitrogen of nitrogen, argon gas or arbitrary proportion and the mist of argon gas.
The preparation method of a kind of lithium-ion-power cell coke powder of the present invention 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 nucleocapsid structure; Described inert atmosphere is argon gas atmosphere.
The preparation method of a kind of lithium-ion-power cell coke powder of the present invention base negative material, in the 5th step, metal is selected from the one in Ag, Cu, Ni, and metal quality is 1 ~ 5% of negative material gross mass.
The present invention adopts said components proportioning and process, with coal-based coke powder for raw material, prepare lithium cell cathode material, technological process is short, preparation cost is low, the product obtained is owing to have employed nucleocapsid structure, uniform and stable bitumencarb coating layer is defined at coal-based coke powder foundation stone ink particle surface, while the high reversible capacity retaining coal-based coke powder foundation stone ink, effectively improve material structure, stop the common embedding of electrolyte and the structure collapses that causes, therefore have that reversible capacity is high, feature that good rate capability, life-span are long.Coal-based coke powder be metallurgical and chemical industry coke production with utilize the byproduct produced in process, be generally used as back to join 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 with coal-based coke powder as the lithium ion battery negative material with high added value prepared by raw material.Solve the recycling problem of the coal-based coke powder of a large amount of low value on the one hand, low cost, high performance lithium ionic cell cathode material can be obtained on the other hand, meet the growing market demand, will very large economic benefit and social benefit be brought.
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 feature itself with certain degree of graphitization, through purifying, coated, heat treatment, the processing step such as surface modification, obtain the Delanium being applicable to lithium ion battery negative, there is the advantage that discharge capacity is high, good cycle, preparation cost are low, and technique is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
The stereoscan photograph of accompanying drawing 1 negative material prepared by embodiment 1.
The XRD collection of illustrative plates of accompanying drawing 2 negative material prepared by embodiment 1.
The first charge-discharge curve chart of accompanying drawing 3 negative material prepared by embodiment 1.
As can be seen from accompanying drawing 1: prepared by the embodiment of the present invention 1, negative material has typical graphite platelet structure, average grain diameter D50 is 22um, and particle size distribution is between 5-30um, and particle size distribution range is narrow.
As can be seen from accompanying drawing 2: three diffraction maximums (002,100,004) significantly characterizing graphite charcoal have appearred in the XRD collection of illustrative plates of negative material prepared by the embodiment of the present invention 1, indicate the crystallinity that material is good.
As can be seen from accompanying drawing 3: the first charge-discharge platform of negative material prepared by the embodiment of the present invention 1 is long and gently, reversible capacity reaches 356.4mAh/g first, and initial coulomb efficiency is 92.3%, symbolizes 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 graphitization, shell is formed by coal tar pitch RESEARCH OF PYROCARBON and at shell layer surface chemical plating metal Ag, negative material fixed carbon content 99.00%, the mass fraction of metal A g is 1%, D50 is 22um, minimum particle size 5um, maximum particle size 30um, tap density is 1.1g/cm
3.
With coal-based coke powder for the preparation method of lithium-ion-power cell coke powder base negative material prepared by raw material, comprise the following steps:
(1) by average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, dry 24h at 120 DEG C in blast furnace, be then ground into average grain diameter 20 μm with eddy airstream pulverizer, classification goes out the particle of particle size range 5-30 μm.
(2) be that 19% hydrofluoric acid solution leaches by the material mass concentration meeting particle size range, control reaction condition is liquid-solid mass ratio is 3:1, and reaction temperature is 25 DEG C, and the processing time is 1h, reacted coke powder is dry to neutrality through washing, and the purifying coke powder purity obtained is 99.6%.
(3) at high-purity coal-based coke powder Surface coating coal tar pitch, first 100g coal tar pitch is dissolved in 500mL toluene and forms coated solution; Then join in coated solution by 1000g purifying coke powder, namely mechanical agitation evenly obtains mixed solution; Finally at 60 DEG C, evaporate mixed solution, removing toluene solvant, obtains the purifying coke powder that coal tar pitch is coated.
(4) take the purifying coke powder 500g that coal tar pitch is coated, add boron oxide 10g, after mixing, be positioned in superhigh temperature graphitizing furnace, at 2800 DEG C, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after graphitization processing.
(5) enclose metal A g on clad material surface, first by clad material at SnCl
2sensitization 1 ~ 2min after heat water rinse in solution, after then drying and the clad material of cooling by 1% loading than being added in the chemical plating fluid for preparing, (it is as follows that chemistry crosses liquid collocation method: first by 2gAgNO
3be dissolved in 60mI H
2in O, and add ammoniacal liquor when constantly stirring, until the Ag separated out
2o precipitation is dissolved completely, then solution blackening again after the NaOH of 2.5g/100mI is added, continue to drip ammoniacal liquor completely limpid to solution, be made into A liquid, separately 45g glucose and 4g tartaric acid are dissolved in 1L water, boil 10min, after cooling, add 100mI ethanol, be made into B liquid, by 1:1 mixing A, B two liquid namely obtain and chemically cross liquid.), in the water bath with thermostatic control of 30 DEG C after stirring reaction 1h, by this suspension filtered, be washed to neutrality, after being placed in the dry 12h of vacuum drying chamber of 170 DEG C, obtain lithium-ion-power cell 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: by gained coke powder base negative material, conductive acetylene, black and binding agent PVDF is mixed and made into electrode slice with mass percent 85:5:5, and with metal lithium sheet form the electrochemistry of half-cell test material embedding/take off lithium performance, electrolyte is commercially available 1M LiPF
6/ EC+DMC solution.Utilize Land battery test system at room temperature to carry out constant current charge-discharge performance test to above-mentioned half-cell, charge-discharge magnification is 0.2C(74mA/g) and 1C(372mA/g), charging/discharging voltage scope is 0.01-2V.The charging and discharging curve of Fig. 3 artificial plumbago negative pole material prepared by the present embodiment, the various performance parameters of negative material is in table 1.
Embodiment 2:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after graphitization, shell is formed by coal tar pitch RESEARCH OF PYROCARBON and at shell layer surface chemical plating metal Cu, negative material fixed carbon content 98.00%, the mass fraction of Ni metal is 2%, D50 is 17um, minimum particle size 5um, maximum particle size 30um, tap density is 1.18g/cm
3.
With coal-based coke powder for the preparation method of lithium-ion-power cell coke powder base negative material prepared by raw material, comprise the following steps:
(1) by average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, dry 24h at 130 DEG C in blast furnace, be then ground into average grain diameter 15 μm with eddy airstream pulverizer, classification goes out the particle of particle size range 5-30 μm.
(2) be that 19% hydrofluoric acid solution leaches by the material mass concentration meeting particle size range, control reaction condition is liquid-solid mass ratio is 3:1, and reaction temperature is 25 DEG C, and the processing time is 1h, reacted coke powder is dry to neutrality through washing, and the purifying coke powder purity obtained is 99.7%.
(3) at high-purity coal-based coke powder Surface coating coal tar pitch, first 100g coal tar pitch is dissolved in 400mL kerosene and forms coated solution; Then join in coated solution by 1000g purifying coke powder, namely mechanical agitation evenly obtains mixed solution; Finally at 80 DEG C, evaporate mixed solution, removing kerosene solvent, obtains the purifying coke powder that coal tar pitch is coated.
(4) take the purifying coke powder 500g that coal tar pitch is coated, add boron oxide 10g, after mixing, be positioned in superhigh temperature graphitizing furnace, at 2800 DEG C, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after graphitization processing.
(5) Ni metal particle is enclosed on clad material surface, first by the SnCl of clad material at 100g/L
2sensitization 1 ~ 2min after heat water rinse in solution, after then drying and the clad material of cooling by 2% loading than being added in the chemical plating fluid for preparing, (it is composed as follows that chemistry crosses liquid: CuSO
45HO
215g/L, CH
2o (37%) 12mL/L, Na
2eDTA30g/L, (C
5h
4n)
20.1g/L, NaOH adjust pH to 12 ~ 13), in the water bath with thermostatic control of 30 DEG C after stirring reaction 1h, by this suspension filtered, be washed to neutrality, put in 380 DEG C of hydrogen atmospheres and be incubated 5h, after stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result is in table 1.
Embodiment 3:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after graphitization, shell is formed by coal tar pitch RESEARCH OF PYROCARBON and at shell layer surface chemical plating metal Ni, negative material fixed carbon content 96.00%, the mass fraction of metallic Ni particles is 4%, D50 is 22um, minimum particle size 5um, maximum particle size 30um, tap density is 1.1g/cm
3.
With coal-based coke powder for the preparation method of lithium-ion-power cell coke powder base negative material prepared by raw material, comprise the following steps:
(1) by average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, dry 12h at 140 DEG C in blast furnace, be then ground into average grain diameter 20 μm with eddy airstream pulverizer, classification goes out the particle of particle size range 5-30 μm.
(2) be that 30% hydrofluoric acid and hydrochloric acid mixed solution leach by the material mass concentration meeting particle size range, hydrofluoric acid and hydrochloric acid mass ratio are 1:1, control reaction condition is liquid-solid mass ratio is 5:1, reaction temperature is 35 DEG C, processing time is 2h, reacted coke powder is dry to neutrality through washing, and the purifying coke powder purity obtained is 99.8%.
(3) at high-purity coal-based coke powder Surface coating coal tar pitch, first 100g coal tar pitch is dissolved in 600mL acetone and forms coated solution; Then join in coated solution by 1000g purifying coke powder, namely mechanical agitation evenly obtains mixed solution; Finally at 70 DEG C, evaporate mixed solution, removing acetone solvent, obtains the purifying coke powder that coal tar pitch is coated.
(4) take the purifying coke powder 500g that coal tar pitch is coated, add boron oxide 10g, after mixing, be positioned in superhigh temperature graphitizing furnace, at 2800 DEG C, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after graphitization processing.
(5) metallic Ni particles is enclosed on clad material surface, first by the SnCl of clad material at 100g/L
2sensitization 1 ~ 2min after heat water rinse in solution, after then drying and the clad material of cooling by 4% loading than being added in the chemical plating fluid for preparing, (it is composed as follows that chemistry crosses liquid: NiCl
26H
2o30g/L, NH
4cl50g/L, natrium citricum 85g/L, inferior sodium phosphate 15g/L, ammoniacal liquor adjusts pH to 8.5 ~ 9), in the water bath with thermostatic control of 90 DEG C after stirring reaction 1h, by this suspension filtered, be washed to neutrality, be placed in 380 DEG C of hydrogen atmospheres and be incubated 5h, after stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result is in table 1.
Embodiment 4:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after graphitization, shell is formed by coal tar pitch RESEARCH OF PYROCARBON and at shell layer surface chemical plating metal Ni, negative material fixed carbon content 95.00%, the mass fraction of metallic Ni particles is 5%, D50 is 27um, minimum particle size 5um, maximum particle size 30um, tap density is 1.15g/cm
3.
With coal-based coke powder for the preparation method of lithium-ion-power cell coke powder base negative material prepared by raw material, comprise the following steps:
(1) by average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, dry 24h at 140 DEG C in blast furnace, be then ground into average grain diameter 25 μm with eddy airstream pulverizer, classification goes out the particle of particle size range 5-30 μm.
(2) be that 30% hydrofluoric acid and sulfuric acid mixed solution leach by the material mass concentration meeting particle size range, hydrofluoric acid and sulfuric acid mass ratio are 1:1, control reaction condition is liquid-solid mass ratio is 3:1, reaction temperature is 25 DEG C, processing time is 1h, reacted coke powder is dry to neutrality through washing, and the purifying coke powder purity obtained is 99.7%.
(3) at high-purity coal-based coke powder Surface coating coal tar pitch, first 100g coal tar pitch is dissolved in 500mL toluene and forms coated solution; Then join in coated solution by 1000g purifying coke powder, namely mechanical agitation evenly obtains mixed solution; Finally at 70 DEG C, evaporate mixed solution, removing toluene solvant, obtains the purifying coke powder that coal tar pitch is coated.
(4) take the purifying coke powder 500g that coal tar pitch is coated, add boron oxide 10g, after mixing, be positioned in superhigh temperature graphitizing furnace, at 2800 DEG C, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after graphitization processing.
(5) metallic Ni particles is enclosed on clad material surface, first by the SnCl of clad material at 100g/L
2sensitization 1 ~ 2min after heat water rinse in solution, after then drying and the clad material of cooling by 5% loading than being added in the chemical plating fluid for preparing, (it is composed as follows that chemistry crosses liquid: NiCl
26H
2o30g/L, NH
4cl50g/L, natrium citricum 85g/L, inferior sodium phosphate 15g/L, ammoniacal liquor adjusts pH to 8.5 ~ 9), in the water bath with thermostatic control of 90 DEG C after stirring reaction 1h, by this suspension filtered, be washed to neutrality, be placed in 380 DEG C of hydrogen atmospheres and be incubated 5h, after stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result is in table 1.
Embodiment 5:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after graphitization, shell is formed by coal tar pitch RESEARCH OF PYROCARBON and at shell layer surface chemical plating metal Cu, negative material fixed carbon content 97.00%, the mass fraction of Ni metal particle is 3%, D50 is 17um, minimum particle size 5um, maximum particle size 30um, tap density is 1.18g/cm
3.
With coal-based coke powder for the preparation method of lithium-ion-power cell coke powder base negative material prepared by raw material, comprise the following steps:
(1) by average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, dry 24h at 130 DEG C in blast furnace, be then ground into average grain diameter 15 μm with eddy airstream pulverizer, classification goes out the particle of particle size range 5-30 μm.
(2) be that 30% hydrofluoric acid and hydrochloric acid mixed solution leach by the material mass concentration meeting particle size range, hydrofluoric acid and hydrochloric acid mass ratio are 1:1, control reaction condition is liquid-solid mass ratio is 4:1, reaction temperature is 40 DEG C, processing time is 2h, reacted coke powder is dry to neutrality through washing, and the purifying coke powder purity obtained is 99.9%.
(3) at high-purity coal-based coke powder Surface coating coal tar pitch, first 100g coal tar pitch is dissolved in 400mL kerosene and forms coated solution; Then join in coated solution by 1000g purifying coke powder, namely mechanical agitation evenly obtains mixed solution; Finally at 80 DEG C, evaporate mixed solution, removing kerosene solvent, obtains the purifying coke powder that coal tar pitch is coated.
(4) take the purifying coke powder 500g that coal tar pitch is coated, add boron oxide 20g, after mixing, be positioned in superhigh temperature graphitizing furnace, at 2800 DEG C, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain the clad material after graphitization processing.
(5) Ni metal particle is enclosed on clad material surface, first by clad material sensitization 1 ~ 2min after heat water rinse in the SnCl2 solution of 100g/L, after then drying and the clad material of cooling by 3% loading than being added in the chemical plating fluid for preparing, (it is composed as follows that chemistry crosses liquid: CuSO
45HO
215g/L, CH
2o (37%) 12mL/L, Na
2eDTA30g/L, (C
5h
4n)
20.1g/L, NaOH adjust pH to 12 ~ 13), in the water bath with thermostatic control of 30 DEG C after stirring reaction 1h, by this suspension filtered, be washed to neutrality, put in 380 DEG C of hydrogen atmospheres and be incubated 5h, after stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result is in table 1.
Embodiment 6:
A kind of lithium-ion-power cell coke powder base negative material, its core is coke powder after graphitization, shell is formed by coal tar pitch RESEARCH OF PYROCARBON and at shell layer surface chemical plating metal Ni, negative material fixed carbon content 96.00%, the mass fraction of metallic Ni particles is 4%, D50 is 22um, minimum particle size 5um, maximum particle size 30um, tap density is 1.1g/cm3.
With coal-based coke powder for the preparation method of lithium-ion-power cell coke powder base negative material prepared by raw material, comprise the following steps:
(1) by average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, dry 12h at 140 DEG C in blast furnace, be then ground into average grain diameter 20 μm with eddy airstream pulverizer, classification goes out the particle of particle size range 5-30 μm.
(2) be that 30% hydrofluoric acid and hydrochloric acid mixed solution leach by the material mass concentration meeting particle size range, hydrofluoric acid and hydrochloric acid mass ratio are 2:1, control reaction condition is liquid-solid mass ratio is 4:1, reaction temperature is 40 DEG C, processing time is 2h, reacted coke powder is dry to neutrality through washing, and the purifying coke powder purity obtained is 99.9%.
(3) at high-purity coal-based coke powder Surface coating coal tar pitch, first 100g coal tar pitch is dissolved in 600mL acetone and forms coated solution; Then join in coated solution by 1000g purifying coke powder, namely mechanical agitation evenly obtains mixed solution; Finally at 70 DEG C, evaporate mixed solution, removing acetone solvent, obtains the purifying coke powder that coal tar pitch is coated.
(4) take the purifying coke powder 500g that coal tar pitch is coated, add boron oxide 20g, after mixing, be positioned in superhigh temperature graphitizing furnace, at 2600 DEG C, carry out graphitization processing, temperature retention time 50min, naturally cool to room temperature, obtain the clad material after graphitization processing.
(5) metallic Ni particles is enclosed on clad material surface, first by the SnCl of clad material at 100g/L
2sensitization 1 ~ 2min after heat water rinse in solution, after then drying and the clad material of cooling by 4% loading than being added in the chemical plating fluid for preparing, (it is composed as follows that chemistry crosses liquid: NiCl
26H
2o30g/L, NH
4cl50g/L, natrium citricum 85g/L, inferior sodium phosphate 15g/L, ammoniacal liquor adjusts pH to 8.5 ~ 9), in the water bath with thermostatic control of 90 DEG C after stirring reaction 1h, by this suspension filtered, be washed to neutrality, be placed in 380 DEG C of hydrogen atmospheres and be incubated 5h, after stove cooling, obtain lithium-ion-power cell coke powder base negative material.
Detect: with embodiment 1.Test result is in table 1.
Comparative example 1:
By average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, dry 12h at 105 DEG C in blast furnace, is then ground into average grain diameter 20 μm with eddy airstream pulverizer.Be that 30% hydrofluoric acid and hydrochloric acid mixed solution leach by material mass concentration, hydrofluoric acid and hydrochloric acid mass ratio are 1:1, control reaction condition is liquid-solid mass ratio is 4:1, reaction temperature is 40 DEG C, processing time is 2h, reacted coke powder is dry to neutrality through washing, and the purifying coke powder purity obtained is 99.8%.Take purifying coke powder 500g, add boron oxide 10g, after mixing, be positioned in superhigh temperature graphitizing furnace, at 2800 DEG C, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain man-made graphite cathode material for lithium ion battery.Detect: with embodiment 1.Test result is in table 1.
Comparative example 2:
By average grain diameter 0.5mm, the coal-based coke powder of content of ashes 11%, dry 12h at 105 DEG C in blast furnace, be then ground into average grain diameter 20 μm with eddy airstream pulverizer, classification goes out the particle of particle size range 5-30 μm.Be that 30% hydrofluoric acid and hydrochloric acid mixed solution leach by the material mass concentration meeting particle size range, hydrofluoric acid and hydrochloric acid mass ratio are 1:1, control reaction condition is liquid-solid mass ratio is 4:1, reaction temperature is 40 DEG C, processing time is 2h, reacted coke powder is dry to neutrality through washing, and the purifying coke powder purity obtained is 99.8%.Take purifying coke powder 500g, be positioned in superhigh temperature graphitizing furnace, at 2800 DEG C, carry out graphitization processing, temperature retention time 20min, naturally cool to room temperature, obtain man-made graphite cathode material for lithium ion battery.Detect: with embodiment 1.Test result is in table 1.
Table 1
As can be seen from Table 1, when coke powder foundation stone ink material prepared by the present invention is for lithium-ion-power cell, discharge capacity is high first, coulombic efficiency is good first; undamped after little circulation 100 times, high rate during charging-discharging is good, shows good high rate performance and cyclical stability.
Claims (8)
1. a lithium-ion-power cell coke powder base negative material, be made up of 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 is by the coal tar pitch RESEARCH OF PYROCARBON after graphitization processing and form at shell layer surface chemical plating metal; The preparation method of described coke powder base negative material, comprises the following steps:
The first step: the coal-based coke powder of raw material is dry, broken, classification
Coal-based for raw material coke powder is carried out drying, fragmentation and classification;
Second step: coal-based coke powder removal of impurities
Mixed with acid solution by coal-based for first step gained coke powder and size mixing, control reaction condition, after making the silicon dioxide in coke powder, iron oxide, alumina impurities and acid reaction, washing is dry, obtains pure coal-based coke powder;
Described acid solution by hydrofluoric acid and at least one in hydrochloric acid, sulfuric acid, salpeter solution in mass ratio 1:1 ~ 5:1 mix and form, acid solution mass percentage concentration is 15-35%; Reaction condition is: temperature 20-60 DEG C, time 1-10h; Mixing the liquid-solid mass ratio of sizing mixing is 2:1 ~ 10:1;
3rd step: high-purity coal-based coke powder Surface coating coal tar pitch
Pure for second step gained coal-based coke powder is immersed in coal tar pitch solution, stirs and obtain mixed solution, the solvent of less than 100 DEG C evaporation removing mixed solutions, obtain with high-purity coal-based coke powder be core, the coal tar pitch nucleocapsid structure that is shell;
4th step: nucleocapsid structure graphitization processing
In the 3rd step gained nucleocapsid structure, add the compound of boron or boron as catalyst, be heated to 2200-2800 DEG C of insulation 10min-2h in an inert atmosphere, carry out graphitization processing;
5th step: surface chemical plating
By the nucleocapsid structure surface chemical metal plating of the 4th step gained through graphitization processing.
2. a kind of lithium-ion-power cell coke powder base negative material according to claim 1, 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%.
3. a kind of lithium-ion-power cell coke powder base negative material according to claim 1, is characterized in that: described negative material mean particle size D
50be 10 ~ 30 μm, minimum particle size is more than or equal to 5 μm, and maximum particle size is less than or equal to 30 μm, tap density 1.1 ~ 1.5g/cm
3.
4. a kind of lithium-ion-power cell coke powder base negative material according to claim 1, it is characterized in that: in the first step, described carries out drying, fragmentation and classification to coal-based coke powder, be by coal-based for raw material coke powder after 120 ~ 150 DEG C of dry 24h, on airflow crash classifying equipoment, carry out fragmentation and classification again, obtain mean particle size D
50be 10 ~ 30 μm, minimum particle size is more than or equal to 5 μm and is less than or equal to the coal-based coke powder of 30 μm with maximum particle size.
5. a kind of lithium-ion-power cell coke powder base negative material according to claim 1, it is characterized in that: in the 3rd step, described coal tar pitch solution is saturated solution, and solvent is selected from least one in toluene, kerosene, pyridine, acetone, carbon disulfide; The amount that the liquid-solid ratio of described mixed solution is 1:10 ~ 1:2 by the mass ratio of coal tar pitch and purifying coke powder is determined; Described mixed solution is evaporation of solvent at 60 ~ 80 DEG C, obtain with high-purity coal-based coke powder be core, the coated purifying coke powder nucleocapsid structure of the coal tar pitch coal tar pitch that is shell.
6. a kind of lithium-ion-power cell coke powder base negative material according to claim 1, it is characterized in that: in the 4th step, the compound of described boron or boron is selected from least one in boron simple substance, boron oxide, boron nitride, boron carbide, boric acid, borate, and the addition of the compound of boron or boron accounts for the 0.5-10% of high-purity coal-based coke powder mass percent in nucleocapsid structure; Described inert atmosphere is the nitrogen of nitrogen, argon gas or arbitrary proportion and the mist of argon gas.
7. a kind of lithium-ion-power cell coke powder base negative material according to claim 6, 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 nucleocapsid structure; Described inert atmosphere is argon gas atmosphere.
8. a kind of lithium-ion-power cell coke powder base negative material according to claim 1, it is characterized in that: in the 5th step, metal is selected from the one in Ag, Cu, Ni, metal quality is 1 ~ 5% of negative material gross mass.
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