CN103560247A - Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof - Google Patents
Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to a vehicle-mounted and energy-storage lithium ion battery cathode material, a battery and a preparation method of the material. Compared with the prior art, the preparation method has the advantage that nanometer conductive carbon is coated on and embedded in the surface of a graphite particle by adopting a mechanical and physical grinding modifying method. According to the preparation method, the use efficiency of a conductive agent and the stability of the conductive agent on the surface of a material can be improved, and thus the compatibility of a cathode active material and electrolyte is improved, and the low-temperature performance and the rate capability of a lithium ion battery is improved. The first-time charge and discharge efficiency of the vehicle-mounted and energy-storage lithium ion battery cathode material reaches up to above 94.0 percent, and the 25-DEG C low-temperature raising rate is higher than 98.0 percent and is increased by above 8.0 percent in comparison with that in the prior art. The preparation method provided by the invention is simple to operate, easy to control and low in production cost, and is suitable for industrialized production.
Description
Technical field
The present invention relates to lithium ion battery material field, particularly, the present invention relates to kind of a vehicle-mounted and energy storage lithium ion battery cathode material and its preparation method.
Background technology
At present, commercial li-ion cell negative electrode material be take graphite type material as main, graphite reaches 372mAh/g as the theoretical specific capacity of negative material, but it exist charge-discharge magnification poor performance, with the shortcoming such as poor, the poor performance at low temperatures of electrolyte compatibility, these all directly have influence on lithium ion battery at the development process in power and energy-storage battery field.
By graphite type material is coated to modification, can make reversible capacity, the cycle performance of material and be promoted significantly with the compatibility of electrolyte, but due to clad material pitch or resin or polymer substance electric conductivity poorer than graphite, therefore the electric conductivity phase strain differential of electrode material, and low temperature high rate performance is bad; Through a large amount of research work, find, conductive agent add the electric conductivity that can effectively improve coated graphite material, the compatibility of electrode material and electrolyte is improved simultaneously.
Electric conducting material add the electric conductivity that can improve to a certain extent graphite material, but it is difficult to exist conductive agent to disperse, the low inferior problem of production efficiency, and scattered conductive agent is as used not in time, also there will be secondary agglomeration phenomenon, thereby affect the service efficiency of conductive agent and the homogeneity of material, cause the circulation of lithium ion battery and high rate performance to reduce.
CN 101887967 A disclose a kind of lithium from the preparation method of cell negative electrode material, comprise the following steps: liquid phase mixes, dry, carbonization treatment, high-temperature process, compound.The preparation method of this negative material comprises carbonization treatment and high-temperature process simultaneously, and mix successively and merge described compound comprising, energy consumption is high, and cost is high, and complicated operation is unfavorable for suitability for industrialized production.
Therefore, develop a kind of electric conductivity, cycle performance and high rate performance excellent, and preparation method is simple, the low lithium of production cost from cell negative electrode material be the technical barrier in affiliated field.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of vehicle-mounted and the preparation method of energy storage with lithium ion battery negative material, comprises the following steps:
(1) adopt organic carbon source to be coated graphite type material, obtain compound;
(2) compound is carried out to carbonization treatment in 500-1800 ℃, obtain the outer graphite material that has unordered structural carbon material coating layer;
(3) material step (2) being obtained and electric conducting material carry out mechanical-physical and grind modification;
(4) sieve, remove magnetic, obtain lithium ion battery negative material.
Preferably, described graphite type material is a kind or the combination of at least 2 kinds in native graphite, Delanium or carbosphere; Preferably, the fixed carbon content of described graphite type material is more than or equal to 99.9%, and axial ratio is 1.0-2.5, and particle mean size is 1-30 μ m, D
max≤ 40.0 μ m, specific area is 2.0-20.0m
2/ g, powder body compacted density is 1.45-2.05g/cm
3; Interlamellar spacing (d
002) be 0.3354-0.3363nm; Diamond structure (3R) content is 1.0-35.0%, I
d/ I
g(Area Ratio) is 0.1-1.0; I
110/ I
004for 0.05-0.95, Lc is 200.0-1000.0nm; La is 800.0-1800.0nm, and magnetisable material content is below 0.5ppm; Metallic foreign body granular size is below 100.0 μ m; In compacted density, be that powder conductivity rate under 1.5g/cc is 50.0-800.0S/cm.
Preferably, described organic carbon source is a kind or the combination of at least 2 kinds in coal tar pitch, petroleum asphalt, mesophase pitch, macromolecular material or polymer.
Preferably, described electric conducting material is conductive nano agent and/or electrically conductive graphite; Preferably, described conductive nano agent is a kind or the combination of at least 2 kinds in CNTs, carbon fiber, nano-graphite or Graphene; Preferably, the average-size (D of described conductive nano agent
50) be 10-600.0nm, specific area SSA is 2.0-60.0m
2/ g; Preferably, the average-size of described conductive nano agent is 10.0-300.0nm; Preferably, the diameter of described CNT and carbon fiber is 1-300nm, and length is 1-20 μ m; Preferably, the graphite flake number of plies of described Graphene is 1-100; Preferably, described conductive nano agent exists with the form of conductive nano liquid; Preferably, in described conductive nano liquid, the content of conductive nano agent is 0.5-20wt%; Preferably, in described conductive nano liquid, dispersion solvent is a kind or the combination of at least 2 kinds in water, methyl alcohol, ethanol, acetone or chloroform.
Preferably, described electric conducting material is a kind or the combination of at least 2 kinds in conduction natural graphite powder, conduction graphous graphite powder or conductive nano carbon black (Super-P); Preferably, in the form of sheets or block, Ratio of long radius to short radius is 1.3-4.5 to described electric conducting material, and average grain diameter is 0.5-12.0 μ m, and specific area SSA is 2.0-60.0m
2/ g.
Preferably, step (1) is described is coated as solid phase is coated or liquid phase coating.
Solid phase of the present invention is coated as affiliated field known technology, and one of ordinary skill in the art can select suitable technical parameter as required.The coated nonrestrictive example of described solid phase comprises: organic carbon source and graphite type material are placed in to mixer, control temperature at 15 ℃-80 ℃, with rotating speed 400-2000rpm, process 1-300min, obtain compound; Described mixer is high speed modification VC mixer, cone-type mixer or kneading machine.
Liquid phase coating of the present invention is affiliated field known technology, and one of ordinary skill in the art can select suitable technical parameter as required.The nonrestrictive example of described liquid phase coating comprises: organic carbon source is joined in solvent, adopt homogenizer to carry out liquid phase mixing, speed of agitator is 3000-5000rpm, mixing time is 20-60min, temperature is 80-90 ℃, then graphite substrate material is joined in said mixture, the mass ratio of organic carbon source and graphite substrate material is 1:9-2:8, continue to adopt homogenizer to carry out liquid phase mixing, speed of agitator is 3000-5000rpm, mixing time is 120-180min, the mass ratio of solvent for use and graphite substrate material is 2～1.2, dry, obtain compound, described solvent is ethanol or methyl alcohol, in described liquid phase coating, the dry spray dryer that adopts carries out, the inlet temperature of spray dryer is 150-350 ℃, outlet temperature is 20-250 ℃, and pressure is 10-100MPa, and charging frequency is 10-100Hz, speed of agitator is 3000-5000rpm, mixing time is 120-180min, and the mass ratio of solvent for use and graphite substrate material is 2～1.2, dry, obtain compound, described solvent is ethanol or methyl alcohol.
Preferably, the described carbonization treatment temperature of step (2) is 600-1600 ℃, is particularly preferably 700～1500 ℃.
Preferably, the described mechanical-physical grinding of step (3) modification is that ball-milling treatment, fusion treatment or high speed nano-dispersed are processed; Preferably, the described ball milling modification processing time is more than 5.0min, and processing speed is 200-4000r/min; The described ball milling modification processing time can be 6.0min, 8.0min, 10.0min, 15.0min, 20.0min, 50.0min, 100.0min, 200.0min, 300.0min, 500.0min, 800.0min, 1000.0min, 1100.0min, 1150.0min, 1180.0min, 1190.0min, 1195.0min or 1199.0min etc., preferably 5.0-1200.0min; Described ball milling modification processing speed can be 210r/min, 220r/min, 250r/min, 300r/min, 500r/min, 1000r/min, 1500r/min, 2000r/min, 2500r/min, 3000r/min, 3500r/min, 3800r/min, 3900r/min or 3950r/min etc.; Preferably, the diameter that described ball milling modification is processed the ball adopting is 0.1-3.0mm, and the kind of ball is alumina balls or corundum ball; Preferably, the described fusion treatment time is 20.0-800.0min, and rotating speed is 800-3000r/min, and cavity gap is 0.1-2.0cm, and temperature is 10-80 ℃; Preferably, the described fusion treatment time is 20.0-300.0min; Preferably, described fusion treatment rotating speed is 800-2600r/min; Preferably, the cavity gap of described fusion treatment is 0.1-1.0cm; Preferably, described fusion treatment temperature is 20-60 ℃; Preferably, the described high speed nano-dispersed time is 20.0-1200.0min, and rotating speed is 200-8000r/min; Preferably, described high speed nano-dispersed adopts dispersant; Preferably, the mass ratio of described electric conducting material and dispersant is 1:0.1-1:1, particularly preferably 1:0.3-1:0.8; Preferably, described dispersant is a kind or the combination of at least 2 kinds in sodium carboxymethylcellulose, sodium lignin sulfonate, magnesium lignosulfonate, kayexalate, ammonium polystyrene sulphonate, sodium metnylene bis-naphthalene sulfonate or polyacrylamide.
Preferably, the described magnetic flux density except magnetic of step (4) is 3000-30000Gs, and treatment temperature is 10-80 ℃, except the magnetic time is 10-120s.
Two of object of the present invention is to provide a kind of vehicle-mounted and energy storage lithium ion battery negative material, and described negative material is prepared by the method for the invention,, electronic conductivity high and low temperature high rate performance good with electrolyte wettability and cycle performance excellence.
Described vehicle-mounted and energy storage are comprised of unordered structural carbon material coating layer and electric conducting material outward graphite type material, matrix with lithium ion battery negative material, and electric conducting material applies equably and is embedded into graphite granule surface.
Preferably, described vehicle-mounted and energy storage are 0.1-20.0wt% with the content of electric conducting material in lithium ion battery negative material, further preferred 0.5-18.0wt%, particularly preferably 1-15.0wt%.
Preferably, described vehicle-mounted and energy storage are 0.1-20.0wt% with the content of disordered structure material with carbon element coating layer in lithium ion battery negative material, further preferred 0.5-18.0wt%, particularly preferably 1-15.0wt%;
Preferably, described vehicle-mounted and energy storage are 0.1:100-20.0:100 with the mass ratio of disordered structure material with carbon element coating layer and graphite type material in lithium ion battery negative material, further preferred 0.5:100-18.0:100, particularly preferably 0.5:100-15.0:100.
Preferably, described vehicle-mounted and energy storage are 10:0.01-10:10.0 with the mass ratio of graphite type material in lithium ion battery negative material and electric conducting material, further preferred 10:0.1-10:8.0, particularly preferably 10:0.5-10:6.0.
Three of object of the present invention is to provide a kind of vehicle-mounted and energy storage lithium ion battery, describedly vehicle-mountedly with lithium ion battery, comprises vehicle-mounted and energy storage lithium ion battery negative material of the present invention with energy storage.
Compared with prior art, the present invention adopts mechanical-physical to grind the method for modification, conductive nano agent and/or electrically conductive graphite are evenly applied and are embedded into graphite granule surface, and nano-sized carbon applies and is embedded into graphite granule surface, there will not be secondary agglomeration phenomenon, increased the active force between conductive agent and graphite granule, promote the service efficiency of conductive agent and in the stability of material surface, thereby improve the compatibility of negative electrode active material and electrolyte, improve low temperature and the high rate performance of lithium ion battery.The head effect of negative material of the present invention is more than 94.0%, higher more than 2.0% than prior art sample, and 25 ℃ of low temperature rise rates, higher than 98.0%, improve more than 8.0% than prior art.The inventive method is simple to operate, be easy to control, and production cost is low, be applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 3.
Fig. 2 is the conductivity comparison diagram of the embodiment of the present invention 2 and comparing embodiment 1.
Fig. 3 is the embodiment of the present invention and comparing embodiment cryogenic property comparison diagram.
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 helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
By phosphorus content be more than 99.9%, granularity is the spherical natural graphite of 3-40 μ m, is placed in VC reactor, the petroleum asphalt that to introduce with native graphite mass ratio be 5:100 carries out solid phase mixing, rotating speed is 1200rpm, incorporation time is 90min, obtains compound; Above-mentioned compound, under nitrogen protection, is carried out to carbonization treatment, and 1200 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer native graphite that has unordered structural carbon material coating layer.Have the native graphite of unordered structural carbon material coating layer by the mass ratio of 100:2, to adopt mechanical ball milling to mix with conductive nano agent Graphene outward, wherein the rotating speed of ball mill is 200rpm, and the processing time is 480min.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 11.2 μ m.
Embodiment 2
A certain amount of acrylic resin is added to the water, adopt homogenizer to carry out liquid phase mixing, speed of agitator is 3000rpm, mixing time is 60min, temperature is 90 ℃, then by phosphorus content, be more than 99.9%, granularity is that the block native graphite of 3-40 μ m joins in said mixture, wherein the mass ratio of acrylic resin and native graphite is 15:100, continue to adopt homogenizer to carry out liquid phase mixing, speed of agitator is 3000rpm, mixing time is 180min, the mass ratio of solvent for use water and block native graphite is 200:100, adopt spray dryer to be dried, inlet temperature is 350 ℃, outlet temperature is 150 ℃, pressure is 100MPa, charging frequency is 10Hz, obtain compound, under nitrogen protection, carry out carbonization treatment, 500 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer native graphite that has unordered structural carbon material coating layer.Have the block native graphite of unordered structural carbon material coating layer by the mass ratio of 100:9, to adopt fusion to mix with CNT outward, the rotating speed that wherein merges machine is 2600rpm, and the processing time is 90min.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 8.9 μ m.
Embodiment 3
By phosphorus content be more than 99.9%, granularity is the Delanium of 3-40 μ m, is placed in cone-type mixer, introduces with Delanium quality than carrying out solid phase mixing for the mesophase pitch of 4:100, rotating speed is 50rpm, incorporation time is 300min, obtains compound; Above-mentioned compound, under nitrogen protection, is carried out to carbonization treatment, and 1800 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer Delanium that has unordered structural carbon material coating layer.Have the Delanium of unordered structural carbon material coating layer by the mass ratio of 100:9:0.1, to adopt fusion machine to mix with conduction natural graphite powder, SP outward, the rotating speed that merges machine is 800rpm, and the processing time is 300min.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 14.5 μ m.
Embodiment 4
By phosphorus content be more than 99.9%, granularity is the block native graphite of 3-40 μ m, is placed in VC reactor, the coal tar pitch that to introduce with native graphite mass ratio be 20:100 carries out solid phase mixing, rotating speed is 2000rpm, incorporation time is 60min, obtains compound; Above-mentioned compound, under nitrogen protection, is carried out to carbonization treatment, and 950 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer native graphite that has unordered structural carbon material coating layer.Have native graphite, SP and the dispersant of unordered structural carbon material coating layer to adopt high speed nano-dispersed to mix by the mass ratio of 100:8:3 outward, the rotating speed of its high speed nano-dispersed is 8000rpm, and the processing time is 60min, and dispersant is polyacrylamide.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 17.0 μ m.
Embodiment 5
By phosphorus content be more than 99.9%, granularity is the carbosphere of 3-40 μ m, is placed in cone-type mixer, the coal tar pitch that to introduce with carbosphere mass ratio be 0.1:100 carries out solid phase mixing, rotating speed is 120rpm, incorporation time is 90min, obtains compound; Above-mentioned compound, under nitrogen protection, is carried out to carbonization treatment, and 1500 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer carbosphere that has unordered structural carbon material coating layer.There are carbosphere, conduction natural graphite powder and the dispersant of unordered structural carbon material coating layer to adopt high speed nano-dispersed to mix by the mass ratio of 100:20:8 outward, the rotating speed of its high speed nano-dispersed is 5000rpm, processing time is 90min, and dispersant is sodium carboxymethylcellulose.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 9.8 μ m.
Embodiment 6
A certain amount of poly(ethylene oxide) is joined in dimethylacetylamide, adopt homogenizer to carry out liquid phase mixing, speed of agitator is 5000rpm, mixing time is 20min, temperature is 80 ℃, then by phosphorus content, be more than 99.9%, granularity is that the spherical natural graphite of 3-40 μ m joins in said mixture, wherein the mass ratio of poly(ethylene oxide) and spherical natural graphite is 18:100, continue to adopt homogenizer to carry out liquid phase mixing, speed of agitator is 5000rpm, mixing time is 120min, the mass ratio of solvent for use dimethylacetylamide and spherical natural graphite is 12:100, adopt spray dryer to be dried, inlet temperature is 280 ℃, outlet temperature is 120 ℃, pressure is 80MPa, charging frequency is 30Hz, obtain compound, under nitrogen protection, carry out carbonization treatment, 700 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer native graphite that has unordered structural carbon material coating layer.Have the native graphite of unordered structural carbon material coating layer by the mass ratio of 100:5:3, to adopt ball mill to mix with conduction graphous graphite powder, carbon fiber outward, the rotating speed of ball mill is 1200rpm, and the processing time is 120min.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 13.8 μ m.
Embodiment 7
By phosphorus content be more than 99.9%, granularity is the Delanium of 3-40 μ m, is placed in VC reactor, introduces with Delanium quality than carrying out solid phase mixing for the coal tar pitch of 6:100, rotating speed is 800rpm, incorporation time is 120min, obtains compound; Above-mentioned compound, under nitrogen protection, is carried out to carbonization treatment, and 900 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer Delanium that has unordered structural carbon material coating layer.Have the Delanium of unordered structural carbon material coating layer by the mass ratio of 100:15, to adopt fusion to mix with conduction natural graphite powder outward, the rotating speed that wherein merges machine is 1800rpm, and the processing time is 120min.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 15.3 μ m.
Embodiment 8
By phosphorus content be more than 99.9%, granularity is the block native graphite of 3-40 μ m, is placed in kneading machine, the petroleum asphalt that to introduce with block native graphite mass ratio be 10:100 carries out solid phase mixing, rotating speed is 180rpm, incorporation time is 60min, and temperature is 80 ℃, obtains compound; Above-mentioned compound, under nitrogen protection, is carried out to carbonization treatment, and 1300 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer native graphite that has unordered structural carbon material coating layer.There is the native graphite of unordered structural carbon material coating layer by the mass ratio of 100:12:5, to adopt high speed nano-dispersed to mix with conduction graphous graphite powder, dispersant outward, the rotating speed of its high speed nano-dispersed is 2500rpm, processing time is 240min, and dispersant is ammonium polystyrene sulphonate.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 12.1 μ m.
Comparing embodiment 1
By phosphorus content be more than 99.9%, granularity is the block native graphite of 3-40 μ m, is placed in VC reactor, the petroleum asphalt that to introduce with native graphite mass ratio be 8:100 carries out solid phase mixing, rotating speed is 1200rpm, incorporation time is 120min, obtains compound; Above-mentioned compound, under nitrogen protection, is carried out to carbonization treatment, and 1200 ℃ of temperature, are cooled to room temperature by product afterwards, obtain the outer native graphite that has unordered structural carbon material coating layer.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 12.5 μ m.
Comparing embodiment 2
By the mass ratio of 100:3, adopt mechanical ball milling to mix with conductive nano agent SP the spherical natural graphite that phosphorus content is more than 99.9%, granularity is 3-40 μ m, wherein the rotating speed of ball mill is 1200rpm, and the processing time is 120min.Gains are sieved, remove magnetic, and except magnetic number of times is 3 times, magnetic flux density is 10000Gs, and treatment temperature is 10 ℃, and electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 14.6 μ m.
The present invention adopts mechanically modifying method, as can be seen from Figure 1, conductive agent is dispersed in coated graphite material surface, can greatly improve the service efficiency of conductive agent and in the stability of material surface, thereby improve the compatibility performance of negative electrode active material and electrolyte, improve low temperature and the high rate performance of lithium ion battery.
Vehicle-mounted and energy storage lithium ion battery negative material prepared by the inventive method, due to conductive agent add and dispersed, as can be seen from Figure 2, the comparing embodiment 1 that the conductivity of the coated graphite material that employing mechanically modifying is processed is obviously better than not adding conductive agent, conductivity increases by 60-180S/cm on a year-on-year basis.
The present invention adopts mechanically modifying method, as can be seen from Figure 3, conductive agent dispersed improved the service efficiency of conductive agent and greatly in the stability of material surface, improved the cryogenic property of lithium ion battery, the cryogenic property of all embodiment is all better than comparing embodiment 1 and 2,25 ℃ of low temperature rise rates of all embodiment, higher than 98.0%, improve more than 8.0% than prior art.
Vehicle-mounted and energy storage lithium ion battery negative material prepared by the inventive method, pattern adopts S:4800 surface sweeping Electronic Speculum instrument to record, and conductivity adopts MCP-PD51 powder conductivity rate mensuration system to record.
The half-cell performance of lithium ion battery negative material for vehicle-mounted and energy storage prepared by the conventional method of evaluating detection method detection embodiment and comparing embodiment of application.
The half-cell result of each embodiment and comparing embodiment is by shown in list below 1.
Table 1
The present invention's full battery testing method used is: take embodiment 1-8 and comparing embodiment 1-2 is negative material, CMC and SBR are binding agent, Super-P is conductive agent, three's mass ratio is negative material: binding agent: conductive agent=95.8:3.2:1.0, the Copper Foil of take carries out smear as collector, and drying, compressing tablet, cut-parts obtain negative plate.Again with LiCoO
2for positive electrode, take PVDF as binding agent, Super-P is conductive agent, three's mass ratio is positive electrode: binding agent: conductive agent=94.5:1.5:4.0, take aluminium foil as collector carries out smear, through conventional method oven dry, compressing tablet, cut-parts, obtain positive plate.By the above-mentioned positive/negative plate matching, take (PE or PP) be barrier film, press positive pole/barrier film/negative pole, top-down order is put well, is then wound into rate cylinder 18650 battery cores.Battery core packs in box hat, after sealing, in dry argon gas glove box, from battery core liquid injection port, injects appropriate electrolyte (lmol/L LiPF6/DMC+EMC+EC, 1:1:1).Open formation, 0.1C speed is charged to 50%S ℃, places after 4-6h, then charges and discharge 3 weeks with 1C, obtain 25 ℃ of battery capacities, then adopt normal temperature 0.5C to fill, low temperature (30 ℃ ,-20 ℃ ,-10 ℃) 0.5C is put, after low-temperature test completes, battery is discharged and recharged once at normal temperatures, calculate low temperature rise rate.Concrete outcome is as shown in table 2.
Adopt and calculate with the following method the low temperature rate of bringing back to life:
Low temperature 25 ℃ of battery rise capacity * 100% after the front 25 ℃ of battery capacity/low-temperature tests of rate=low-temperature test of bringing back to life.
Table 2
| Negative material | -10℃/25℃ | -20℃/25℃ | -30℃/25℃ | 25 ℃ of rise rates |
| Embodiment 1 | 92.90% | 81.50% | 65.70% | 98.7% |
| Embodiment 2 | 94.90% | 84.00% | 68.40% | 98.6% |
| Embodiment 3 | 95.20% | 86.50% | 72.90% | 98.7% |
| Embodiment 4 | 96.70% | 89.80% | 74.20% | 98.8% |
| Embodiment 5 | 96.10% | 87.20% | 73.90% | 98.9% |
| Embodiment 6 | 94.90% | 85.90% | 68.70% | 98.6% |
| Embodiment 7 | 95.00% | 84.80% | 67.90% | 98.9% |
| Embodiment 8 | 92.80% | 82.20% | 66.90% | 98.4% |
| Comparing embodiment 1 | 82.80% | 65.30% | 45.30% | 85.0% |
| Comparing embodiment 2 | 89.60% | 72.80% | 48.90% | 89.3% |
Applicant's statement, 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, 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 the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for lithium ion battery negative material for vehicle-mounted and energy storage, comprises the following steps:
(1) adopt organic carbon source to be coated graphite type material, obtain compound;
(2) compound is carried out to carbonization treatment in 500-1800 ℃, obtain the outer graphite material that has unordered structural carbon material coating layer;
(3) material step (2) being obtained and electric conducting material carry out mechanical-physical and grind modification;
(4) sieve, remove magnetic, obtain lithium ion battery negative material.
2. the method for claim 1, is characterized in that, described graphite type material is a kind or the combination of at least 2 kinds in native graphite, Delanium or carbosphere; Preferably, the fixed carbon content of described graphite type material is more than or equal to 99.9%, and axial ratio is 1.0-2.5, and particle mean size is 1-30 μ m, D
max≤ 40.0um, specific area is 2.0-20.0m
2/ g, powder body compacted density is 1.45-2.05g/cm
3; Interlamellar spacing is 0.3354-0.3363nm; Diamond structure content is 1.0-35.0%, I
d/ I
gfor 0.1-1.0; I
110/ I
004for 0.05-0.95, Lc is 200.0-1000.0nm; La is 800.0-1800.0nm, and magnetisable material content is below 0.5ppm; Metallic foreign body granular size is below 100.0 μ m; In compacted density, be that powder conductivity rate under 1.5g/cc is 50.0-800.0S/cm.
3. method as claimed in claim 1 or 2, is characterized in that, described organic carbon source is a kind or the combination of at least 2 kinds in coal tar pitch, petroleum asphalt, mesophase pitch, macromolecular material or polymer;
Preferably, described electric conducting material is conductive nano agent and/or electrically conductive graphite; Preferably, described conductive nano agent is a kind or the combination of at least 2 kinds in CNTs, carbon fiber, nano-graphite or Graphene; Preferably, the average-size of described conductive nano agent is 10-600.0nm, and specific area SSA is 2.0-60.0m
2/ g; Preferably, the average-size of described conductive nano agent is 10.0-300.0nm; Preferably, the diameter of described CNT and carbon fiber is 1-300nm, and length is 1-20 μ m; Preferably, the graphite flake number of plies of described Graphene is 1-100; Preferably, described conductive nano agent exists with the form of conductive nano liquid; Preferably, in described conductive nano liquid, the content of conductive nano agent is 0.5-20wt%; Preferably, in described conductive nano liquid, dispersion solvent is a kind or the combination of at least 2 kinds in water, methyl alcohol, ethanol, acetone or chloroform.
4. the method as described in claim 1-3 any one, is characterized in that, described electric conducting material is a kind or the combination of at least 2 kinds in conduction natural graphite powder, conduction graphous graphite powder or conductive nano carbon black; Preferably, in the form of sheets or block, Ratio of long radius to short radius is 1.3-4.5 to described electric conducting material, and average grain diameter is 0.5-12.0 μ m, and specific area SSA is 2.0-60.0m
2/ g.
5. the method as described in claim 1-4 any one, is characterized in that, step (1) is described to be coated as solid phase is coated or liquid phase coating;
The described carbonization treatment temperature of step (2) is 600-1600 ℃, is particularly preferably 700～1500 ℃.
6. the method as described in claim 1-5 any one, is characterized in that, it is that ball-milling treatment, fusion treatment or high speed nano-dispersed are processed that the described mechanical-physical of step (3) grinds modification; Preferably, the described ball milling modification processing time is more than 5.0min, and processing speed is 200-4000r/min; Preferably, the described ball milling modification processing time is 5.0-1200.0min; Preferably, the diameter that described ball milling modification is processed the ball adopting is 0.1-3.0mm, and the kind of ball is alumina balls, zirconia or corundum ball; Preferably, the described fusion treatment time is 20.0-800.0min, and rotating speed is 800-3000r/min, and cavity gap is 0.1-2.0cm, and temperature is 10-80 ℃; Preferably, the described fusion treatment time is 20.0-300.0min; Preferably, described fusion treatment rotating speed is 800-2600r/min; Preferably, the cavity gap of described fusion treatment is 0.1-1.0cm; Preferably, described fusion treatment temperature is 20-60 ℃; Preferably, the described high speed nano-dispersed time is 20.0-1200.0min, and rotating speed is 200-8000r/min; Preferably, described high speed nano-dispersed adopts dispersant; Preferably, the mass ratio of described electric conducting material and dispersant is 1:0.1-1:1, particularly preferably 1:0.3-1:0.8; Preferably, described dispersant is a kind or the combination of at least 2 kinds in sodium carboxymethylcellulose, sodium lignin sulfonate, magnesium lignosulfonate, kayexalate, ammonium polystyrene sulphonate, sodium metnylene bis-naphthalene sulfonate or polyacrylamide;
Preferably, the described magnetic flux density except magnetic of step (4) is 3000-30000Gs, and treatment temperature is 10-80 ℃, except the magnetic time is 10-120s.
7. vehicle-mounted and an energy storage lithium ion battery negative material, is characterized in that, described vehicle-mounted and energy storage is prepared by the method described in claim 1-6 any one with lithium ion battery negative material.
8. vehicle-mounted and energy storage lithium ion battery negative material as claimed in claim 7, it is characterized in that, described vehicle-mounted and energy storage are comprised of unordered structural carbon material coating layer and electric conducting material outward graphite type material, matrix with lithium ion battery negative material, and electric conducting material applies equably and is embedded into graphite granule surface.
9. vehicle-mounted and energy storage lithium ion battery negative material as claimed in claim 7 or 8, it is characterized in that, described vehicle-mounted and energy storage are 0.1-20.0wt% with the content of electric conducting material in lithium ion battery negative material, further preferred 0.5-18.0wt%, particularly preferably 1-15.0wt%;
Preferably, described vehicle-mounted and energy storage are 0.1-20.0wt% with the content of disordered structure material with carbon element coating layer in lithium ion battery negative material, further preferred 0.5-18.0wt%, particularly preferably 1-15.0wt%;
Preferably, described vehicle-mounted and energy storage are 0.1:100-20.0:100 with the mass ratio of disordered structure material with carbon element coating layer and graphite type material in lithium ion battery negative material, further preferred 0.5:100-18.0:100, particularly preferably 0.5:100-15.0:100;
Preferably, described vehicle-mounted and energy storage are 10:0.01-10:10.0 with the mass ratio of graphite type material in lithium ion battery negative material and electric conducting material, further preferred 10:0.1-10:8.0, particularly preferably 10:0.5-10:6.0.
10. vehicle-mounted and an energy storage lithium ion battery, is characterized in that, described vehicle-mounted and energy storage comprises the vehicle-mounted and energy storage lithium ion battery negative material as described in claim 7-9 any one with lithium ion battery.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1624955A (en) * | 2003-12-01 | 2005-06-08 | 上海杉杉科技有限公司 | Method for manufacturing carbon nagtive electrode material of lithium ion cell |
| CN1702893A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof |
| CN101147284A (en) * | 2005-03-23 | 2008-03-19 | 日本瑞翁株式会社 | Binder for electrode of nonaqueous electrolyte secondary battery, electrode, and nonaqueous electrolyte secondary battery |
| CN101412510A (en) * | 2007-10-15 | 2009-04-22 | 台湾松下能源股份有限公司 | Composite graphite for lithium secondary battery and manufacturing method thereof |
| CN101887967A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN102473898A (en) * | 2009-07-01 | 2012-05-23 | 日本瑞翁株式会社 | Electrode for secondary battery, slurry for secondary battery electrode, and secondary battery |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004196609A (en) * | 2002-12-19 | 2004-07-15 | Jfe Chemical Corp | Production method for composite graphite particle, composite graphite particle, cathode material for lithium ion secondary battery, and lithium ion secondary battery |
| JP2005097010A (en) * | 2003-09-22 | 2005-04-14 | Showa Denko Kk | Carbon material, production method therefor and its application |
| JP4748949B2 (en) * | 2004-03-31 | 2011-08-17 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| JP4537809B2 (en) * | 2004-09-13 | 2010-09-08 | リグナイト株式会社 | Carbon / phenolic resin composite material, carbon / phenolic resin composite cured material, carbon / phenolic resin composite carbonized material, fuel cell separator, conductive resin composition, battery electrode, electric double layer capacitor |
| JP5143437B2 (en) * | 2007-01-30 | 2013-02-13 | 日本カーボン株式会社 | Method for producing negative electrode active material for lithium ion secondary battery, negative electrode active material, and negative electrode |
| JP2009158105A (en) * | 2007-12-25 | 2009-07-16 | Tokai Carbon Co Ltd | Method of manufacturing composite carbon material for negative electrode material of lithium ion secondary battery |
| EP2403802A4 (en) * | 2009-03-02 | 2015-07-01 | Showa Denko Kk | Composite graphite particles and lithium secondary battery using the same |
| JP5413645B2 (en) * | 2009-03-13 | 2014-02-12 | 東海カーボン株式会社 | Method for producing negative electrode material for lithium secondary battery |
| KR101383967B1 (en) * | 2010-07-02 | 2014-04-10 | 썬쩐 비티아르 뉴 에너지 머티어리얼스 아이엔씨이 | Lithium ion battery negative electrode material and preparing method therefor |
| KR101942599B1 (en) * | 2011-03-29 | 2019-01-25 | 미쯔비시 케미컬 주식회사 | Negative electrode carbon material for non-aqueous secondary battery, negative electrode, and non-aqueous secondary battery |
| KR101907700B1 (en) * | 2011-04-13 | 2018-10-12 | 에스 이 아이 가부시키가이샤 | Electrode material for lithium secondary battery and lithium secondary battery |
| CN103620836B (en) * | 2011-06-30 | 2016-03-23 | 三洋电机株式会社 | Rechargeable nonaqueous electrolytic battery and manufacture method thereof |
| JP2013222641A (en) * | 2012-04-18 | 2013-10-28 | Showa Denko Kk | Negative electrode material for lithium ion battery and application thereof |
-
2013
- 2013-11-08 CN CN201310554920.3A patent/CN103560247B/en active Active
-
2014
- 2014-06-12 KR KR1020140071407A patent/KR20150053693A/en active Search and Examination
- 2014-07-31 JP JP2014156362A patent/JP6152076B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1624955A (en) * | 2003-12-01 | 2005-06-08 | 上海杉杉科技有限公司 | Method for manufacturing carbon nagtive electrode material of lithium ion cell |
| CN101147284A (en) * | 2005-03-23 | 2008-03-19 | 日本瑞翁株式会社 | Binder for electrode of nonaqueous electrolyte secondary battery, electrode, and nonaqueous electrolyte secondary battery |
| CN1702893A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof |
| CN101412510A (en) * | 2007-10-15 | 2009-04-22 | 台湾松下能源股份有限公司 | Composite graphite for lithium secondary battery and manufacturing method thereof |
| CN102473898A (en) * | 2009-07-01 | 2012-05-23 | 日本瑞翁株式会社 | Electrode for secondary battery, slurry for secondary battery electrode, and secondary battery |
| CN101887967A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104124431A (en) * | 2014-08-12 | 2014-10-29 | 湖南元素密码石墨烯研究院（有限合伙） | Graphite negative electrode material for lithium ion battery and preparation method of graphite negative electrode material |
| CN106207180A (en) * | 2016-07-19 | 2016-12-07 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of porous hollow graphite material |
| CN106207180B (en) * | 2016-07-19 | 2019-01-15 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of porous hollow graphite material |
| CN106848468A (en) * | 2017-01-25 | 2017-06-13 | 天津市捷威动力工业有限公司 | A kind of method and apparatus that hard charcoal coated graphite is prepared using the cleaning fluid for reclaiming |
| CN110854371A (en) * | 2019-11-26 | 2020-02-28 | 宁夏百川新材料有限公司 | Carbon composite negative electrode material and preparation method thereof |
| CN115117366A (en) * | 2022-08-29 | 2022-09-27 | 天津凯普瑞特新能源科技有限公司 | Carbon-coated aluminum foil, manufacturing process thereof and lithium ion battery |
| CN115117366B (en) * | 2022-08-29 | 2022-11-18 | 天津凯普瑞特新能源科技有限公司 | Carbon-coated aluminum foil, manufacturing process thereof and lithium ion battery |
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