CN102956889B - Composite cathode material for lithium ion cell and preparation method thereof - Google Patents
Composite cathode material for lithium ion cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of composite cathode material for lithium ion cell and preparation method thereof.Composite cathode material for lithium ion cell of the present invention has " kernel-double casing " gradient-structure.Its preparation method is: ground floor shell isotropic coke pulverized by airslide disintegrating mill or nanon ball-mill is milled between 300nm ~ 3.0 μm, kernel graphite granule, isotropic coke is received dimension particle and binding agent carry out merging, to obtain specific area be 8.0 ~ 60.0m in carbonization
2the presoma material with carbon element of the coated ground floor shell of/g; Carry out secondary fusion again, composite negative pole material that graphitization obtains coated second time shell.The present invention is compared with the prior art, and this composite cathode material for lithium ion cell has good absorbent, very high energy density, high rate performance, and the cryogenic property of excellence and cycle performance; Preparation technology is easy to control, and is applicable to industrialized mass production.
Description
Technical field
The present invention relates to composite negative electrode material of lithium ion battery such as the 3C/3G fields such as a kind of mobile phone, notebook computer, panel computer, e-book and electric bicycle (E-bike), electric automobile (EV), mixed power electric car (HEV) and energy storage field and preparation method thereof.
Background technology
Lithium ion battery is because of features such as its high power capacity, high voltage, small-sized, lightweights, be widely used in the mobile electronic devices such as mobile phone, notebook computer, panel computer, video camera, and the field such as electric bicycle (E-bike), electric automobile (EV), mixed power electric car (HEV) and energy storage.
At present, domestic and international silicon/carbon/graphite in lithium ion batteries class negative material is mainly four major types: natural modified graphite, Delanium, carbonaceous mesophase spherules (being also a kind of Delanium) and composite graphite.Both at home and abroad in this four major types negative material, all there is certain material technology and technology bottleneck can not effectively be broken through, there is gram specific capacity lower, high rate performance and poor performance at low temperatures, the shortcomings such as the cathode pole piece absorbent difference made, especially both at home and abroad ubiquity is difficult to obtain the graphite cathode material (discharging ratio more than 70% under National 863 plan electric automobile power battery Low temperature property requirements-20 DEG C of environment) that the ratio of discharging of 0.2C under-20 DEG C of environment is more than 80% of 23 DEG C of environment discharge capacity, therefore have impact on the further lifting of lithium ion battery especially lithium-ion-power cell performance.
Based on above context analyzer, be badly in need of a kind of gram specific capacity of exploitation between 350 ~ 380mAh/g, pole piece compaction density is at 1.60 ~ 1.90g/cm
3between, cycle performance is excellent, and the capacity after 500 times that circulates still maintains more than 90%; Cryogenic property is excellent especially, under-20 DEG C of environment, 0.2C ratio of discharging is more than 80% of 23 DEG C of environment discharge capacity, the graphite-like composite negative pole material that absorbent is good carrys out the demand of satisfied following high-end market, especially the demand of electric automobile (EV), mixed power electric car (HEV) and energy storage field battery.
Summary of the invention
It is not high that the object of the invention is intended to solve existing composite negative electrode material of lithium ion battery gram specific capacity, the problems of the prior art such as compacted density is lower, pole piece absorbent is poor, poor performance at low temperatures, cycle life are not long, there is provided that the high gram specific capacity of a kind of lithium ion battery, high compacted density, absorbent are good, the composite negative pole material of good rate capability, low temperature performance excellent and good cycle and preparation method thereof, promote the combination property of lithium ion battery.
The present invention is by the following technical solutions: a kind of composite cathode material for lithium ion cell, it is characterized in that: described composite cathode material for lithium ion cell has " kernel-double casing " gradient-structure, wherein kernel is the graphite granule of granularity 3.0 ~ 35.0 μm, and double casing comprises ground floor shell (intermediate layer) and second layer shell (outermost layer); Ground floor shell (intermediate layer) to be bondd coated formation through binding agent by granularity 300nm ~ 3.0 μm Na Wei meter multinuclear graphite granule, and total covering amount is 10.0 ~ 30.0% of whole composite negative pole material quality; Second layer shell (outermost layer) is pitch or resinae coating layer, and covering amount is 5.0 ~ 20.0% of whole composite negative pole material quality.
In composite negative pole material of the present invention, the aggregate Na Wei meter multinuclear graphite granule of ground floor shell (intermediate layer) is isotropic coke, the feature of this isotropic coke own has very little Ratio of long radius to short radius, be 0.8 ~ 1.2, volatile matter is more than 10.0%, and higher volatile matter can guarantee that in technique implementation procedure, obtained ground floor shell has very high specific area and nano-porous structure; It is between μm nanometer to micron of 300nm ~ 3.0 as ground floor shell (intermediate layer) particles of aggregates particle size range, and specific area is 8.0 ~ 60.0m
2/ g, particle surface has nano-porous structure.
In composite negative pole material of the present invention, the binding agent of ground floor shell is resinae or pitch class binding agent.
" kernel-double casing " structure of composite negative pole material of the present invention forms good specific area and grain size characteristic value gradient-structure: (1) specific area is respectively kernel 3.0 ~ 8.0m from inside to outside
2between/g, intermediate layer 8.0 ~ 60.0m
2between/g, outermost layer 0.8 ~ 3.5m
2between/g; (2) granularity is from inside to outside from large (3.0 ~ 35.0 μm) to little (300nm ~ 3.0 μm), finally arrives the coating layer of outside; (3) intermediate layer granulate surface has nano-porous structure.
Composite cathode material for lithium ion cell of the present invention, is characterized in that: described composite negative pole material gram specific capacity is 350 ~ 380mAh/g, and granularity is 3.0 ~ 55.0 μm, and tap density is 1.10 ~ 1.30g/ml, and specific area is 0.8 ~ 3.5m
2/ g, powder body compacted density is 1.70 ~ 2.30g/cm
3.
A kind of preparation method of composite cathode material for lithium ion cell, comprise the following steps: one, ground floor shell (intermediate layer) isotropic coke is carried out air-flow crushing or nanon ball-mill ball milling by airslide disintegrating mill, be crushed to by its grain graininess between μm nanometer to micron of 300nm ~ 3.0, obtained isotropic coke receives dimension rice grain; Two, be the graphite granule (kernel) of 3.0 ~ 35.0 μm by granularity, total covering amount is that 10.0 ~ 30.0% isotropic coke of whole composite negative pole material quality are received dimension rice grain, resinae or pitch class binding agent and solvent and are placed in mixer with the ratio of 0.5 ~ 5.0 liter/Kg, under the rotating speed of 30 ~ 200r/min, mix 30 ~ 180min, obtain mixing emulsion; Three, will mix emulsion in fusion machine, at the rotating speed of 300 ~ 2000r/min, fusion temperature is merge 30 ~ 180min under the condition of 20 ~ 100 DEG C, obtains merging presoma; Four, under inert gas shielding, fusion presoma is placed in high temperature furnace and is warming up to 400 ~ 800 DEG C of charing process 10 ~ 48h with 5 ~ 30 DEG C/min, be then cooled to room temperature with the cooling rate of 5 ~ 30 DEG C/min, obtained specific area is 8.0 ~ 60.0m
2the presoma material with carbon element of the coated ground floor shell of/g; Five, this presoma material with carbon element is added the pitch that covering amount is 5.0 ~ 20.0% of whole composite negative pole material quality or resin, at the rotating speed of 300 ~ 2000r/min, fusion temperature is merge 30 ~ 180min under the condition of 20 ~ 100 DEG C, merge presoma before obtaining graphitization, then carry out graphitization heat treatment at 2800 ~ 3300 DEG C after, obtain the composite cathode material for lithium ion cell of coated second time shell.
A kind of preparing that the solvent used in composite negative pole material is water, in ethanol, isopropyl alcohol, glycerol, acetone, toluene or dimethylbenzene of the present invention or their mixed solvent.
The present invention is when preparing the high-temperature process in composite negative pole material, and the protection inert gas be filled with is the above-mentioned mist of nitrogen, argon gas, helium, neon etc. or any ratio.
A kind of negative electrode for lithium ion battery of the present invention, is characterized in that: be coated in metal collector by mixed uniformly to the composite negative pole material of above-mentioned preparation, binding agent and conductive agent material, and dry and compacting forms.
Negative pole of the present invention, is characterized in that: this negative plate can obtain very high compacted density, reaches 1.60 ~ 1.90g/cm3, thus obtains very high energy density; With the lithium ion battery that this negative pole is made, cycle performance is excellent, and the capacity after 500 times that circulates still maintains more than 90%; Cryogenic property is excellent especially, and under-20 DEG C of environment, 0.2C ratio of discharging is more than 80% of 25 DEG C of environment discharge capacity.
Be compared with the prior art, invention introduces a kind of Novel cathode material for lithium ion battery structure: " kernel-double casing " structure, the introducing of this structure, the bottleneck of lithium ion battery negative material absorbent and poor performance at low temperatures is for a long time solved from the feature of negative material structure own, its " kernel-double casing " structure forms good specific area and grain size characteristic value gradient-structure, and intermediate layer granulate surface has nano-porous structure, thus increased substantially the absorbent of negative material, guarantee that negative material has excellent absorbent, high rate performance, cryogenic property and cycle performance, obtain the composite negative pole material of a kind of gram of specific capacity high-energy-density between 350 ~ 380mAh/g, its obtained cathode pole piece compacted density is up to 1.60 ~ 1.90g/cm3, very high energy density can be obtained, with the lithium ion battery that this negative pole is made, cycle performance is excellent, and the capacity after 500 times that circulates still maintains more than 90%, cryogenic property is excellent especially, and under-20 DEG C of environment, 0.2C ratio of discharging is more than 80% of 23 DEG C of environment discharge capacity.The different demands of 3C/3G high-end field can be met simultaneously, and the demand of electric automobile (EV), mixed power electric car (HEV) and energy storage field lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 2.
Fig. 2 is first three week gram specific capacity test curve of the embodiment of the present invention 2.
Fig. 3 is that the negative plate of the embodiment of the present invention 2 is at compacted density 1.75g/cm
3when lithium ion battery 1C cycle performance test curve.
Embodiment
For further illustrating content of the present invention and feature, be described in detail below in conjunction with embodiment and accompanying drawing.Composite negative pole material of the present invention, has " kernel-double casing " gradient-structure, and wherein kernel is the graphite granule of granularity 3.0 ~ 35.0 μm, and double casing comprises ground floor shell (intermediate layer) and second layer shell (outermost layer); Ground floor shell (intermediate layer) to be bondd coated formation through binding agent by granularity 300nm ~ 3.0 μm Na Wei meter multinuclear graphite granule, and total covering amount is 10.0 ~ 30.0% of whole composite negative pole material quality; Second layer shell (outermost layer) is pitch or resinae coating layer, and covering amount is 5.0 ~ 20.0% of whole composite negative pole material quality.
The aggregate Na Wei meter multinuclear graphite granule of the ground floor shell (intermediate layer) used is isotropic coke, and the feature of this isotropic coke own has very little Ratio of long radius to short radius, and be 0.8 ~ 1.2, volatile matter is more than 10.0%; It is between μm nanometer to micron of 300nm ~ 3.0 as ground floor shell (intermediate layer) particles of aggregates particle size range, and specific area is 8.0 ~ 60.0m
2/ g, particle surface has nano-porous structure.
The binding agent of ground floor shell used is resinae or pitch class binding agent.
The preparation method of composite negative electrode material of lithium ion battery of the present invention, comprises the following steps:
One, ground floor shell (intermediate layer) isotropic coke is carried out air-flow crushing or nanon ball-mill ball milling by airslide disintegrating mill, be crushed to by its grain graininess between μm nanometer to micron of 300nm ~ 3.0, obtained isotropic coke receives dimension rice grain;
Two, be the graphite granule (kernel) of 3.0 ~ 35.0 μm by granularity, total covering amount is that 10.0 ~ 30.0% isotropic coke of whole composite negative pole material quality are received dimension rice grain, resinae or pitch class binding agent and solvent and are placed in mixer with the ratio of 0.5 ~ 5.0 liter/Kg, under the rotating speed of 30 ~ 200r/min, mix 30 ~ 180min, obtain mixing emulsion;
Three, will mix emulsion in fusion machine, at the rotating speed of 300 ~ 2000r/min, fusion temperature is merge 30 ~ 180min under the condition of 20 ~ 100 DEG C, obtains merging presoma;
Four, under inert gas shielding, fusion presoma is placed in high temperature furnace and is warming up to 400 ~ 800 DEG C of charing process 10 ~ 48h with 5 ~ 30 DEG C/min, be then cooled to room temperature with the cooling rate of 5 ~ 30 DEG C/min, obtained specific area is 8.0 ~ 60.0m
2the presoma material with carbon element of the coated ground floor shell of/g;
Five, this presoma material with carbon element is added the pitch that covering amount is 5.0 ~ 20.0% of whole composite negative pole material quality or resin, at the rotating speed of 300 ~ 2000r/min, fusion temperature is merge 30 ~ 180min under the condition of 20 ~ 100 DEG C, merge presoma before obtaining graphitization, then carry out graphitization heat treatment at 2800 ~ 3300 DEG C after, obtain the composite cathode material for lithium ion cell of coated second time shell.
Composite negative electrode material of lithium ion battery prepared by the present invention, Britain Malvern instrument company Malvern-Mastersizer2000 laser particle size analyzer is adopted to measure its average grain diameter, U.S. Kang Ta instrument company Monosorb direct-reading dynamic flow method specific surface area analysis instrument is adopted to survey its specific area, adopt the x-ray diffractometer of Japanese Shimadzu Corporation (XRD-6100) to measure the crystal structure of composite negative pole material, adopt the surface topography of Branch Tech KYKY-2800B ESEM scanning electronic microscope observation composite negative pole material.
Using composite negative electrode material of lithium ion battery of the present invention to prepare negative pole, is be coated in metal collector by mixed uniformly to the composite negative pole material of above-mentioned preparation, binding agent and conductive agent material, and dry and compacting forms.The concrete preparation method's citing of the one of negative pole: by composite negative pole material and binding agent sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) (CMC: SBR=1: 1 mass ratio), conductive carbon black (SuperP), deionized water (composite negative pole material: after CMC: SBR: SuperP=95.0: 1.5: 2.5: 1.0) mixing, be coated in 9 according to a certain percentage
on the Copper Foil that m is thick, coated diaphragm roll-in is obtained negative plate.This negative plate is used for the high rate performance of lithium ion battery resultant battery, cryogenic property and cycle performance test below.
The preparation of resultant battery and high rate performance, cryogenic property and cycle performance test process as follows:
(1) cobalt acid lithium LiCoO is used
2as positive active material, with binding agent polyvinylidene fluoride (PVDF), conductive carbon black (SuperP) according to 94: 3: 3 mass ratio mix and blend form slurry in the 1-METHYLPYRROLIDONE (NMP), be coated on aluminium foil, make positive plate through 85 DEG C of vacuumizes, roll extrusion.
(2) by the barrier film of the PP/PE/PP three-decker of above negative plate, positive plate, U.S. Celgard and 1mol/LLiPF
6+ EC/DMC/EMC (volume ratio 1: 1: 1) electrolyte is assembled into 523450 polymer Li-ion batteries.
(3) cryogenic property is according to the discharge capacity ratio at GB/T18287-2000 " cell phone lithium ion battery generic specification " test-20 DEG C; Cycle performance adopts 1.0C to carry out discharge and recharge, and charging/discharging voltage scope is 4.2V ~ 3.0V; Multiplying power discharging property test for same battery with 1.0C constant current charge to 4.2V, turning constant voltage charge to electric current is less than 0.05C, then respectively with 1.0C and 15.0C constant-current discharge to 3.0V, with 15C/1C
Discharge capacity ratio characterizes high rate performance.Test result is in table 1.
It is as follows that the composite negative pole material of the present invention to preparation carries out first three week gram specific capacity test process:
(1) preparation of cathode pole piece: be 90: 5: 5 in the middle mix and blend form slurry of 1-METHYLPYRROLIDONE (NMP) according to mass ratio by obtained composite negative pole material and conductive carbon black (SuperP), polyvinylidene fluoride (PVDF), be coated on Copper Foil, then by its vacuumize at 120 DEG C in drying box, negative plate is pressed into.
(2) battery assembling: take metal lithium sheet as positive pole, electrolyte adopts 1mol/LLiPF
6the solution of+EC/DMC/EMC (volume ratio 1: 1: 1), barrier film adopts the barrier film of the PP/PE/PP three-decker of U.S. Celgard, in the glove box of logical full argon gas, be assembled into button cell.
(3) button cell adopts following discharge and recharge system to test its capacity and efficiency:
A) constant-current discharge (0.2mA, 0.001V)
B) (10min) is left standstill
C) constant current charge (0.2mA, 2.000V)
Embodiment 1
With airslide disintegrating mill, isotropic coke being crushed to D50 is about 1.0 μm, the water of the isotropic coke particle of graphite granule, whole composite graphite quality 15%, the pitch of whole composite graphite quality 5% and 2L/ kilogram of graphite quality is mixed, under the rotating speed of 100r/min, mix 120min, obtain mixing emulsion; To mix emulsion in fusion machine, at the rotating speed of 1000r/min, fusion temperature is merge 120min under the condition of 60 DEG C, obtains merging presoma; Under argon shield gas, fusion presoma is placed in high temperature furnace and is warming up to 700 DEG C of charing process 16h with 10 DEG C/min, be then cooled to room temperature with the cooling rate of 5 DEG C/min, the presoma material with carbon element of obtained coated ground floor shell; This presoma material with carbon element is added the pitch that covering amount is 10.0% of whole composite negative pole material quality, at the rotating speed of 1000r/min, fusion temperature is merge 120min under the condition of 60 DEG C, merge presoma before obtaining graphitization, then carry out graphitization heat treatment at 3200 DEG C after, obtain the composite cathode material for lithium ion cell of coated second time shell.
Embodiment 2
With nanon ball-mill, isotropic coke being milled to D50 is about 500nm, the water of the isotropic coke particle of graphite granule, whole composite graphite quality 20%, the resin of whole composite graphite quality 8% and 3L/ kilogram of graphite quality is mixed, under the rotating speed of 180r/min, mix 160min, obtain mixing emulsion; To mix emulsion in fusion machine, at the rotating speed of 1600r/min, fusion temperature is merge 60min under the condition of 80 DEG C, obtains merging presoma; Under argon shield gas, fusion presoma is placed in high temperature furnace and is warming up to 600 DEG C of charing process 24h with 5 DEG C/min, be then cooled to room temperature with the cooling rate of 5 DEG C/min, the presoma material with carbon element of obtained coated ground floor shell; This presoma material with carbon element is added the pitch that covering amount is 8.0% of whole composite negative pole material quality, at the rotating speed of 1500r/min, fusion temperature is merge 60min under the condition of 80 DEG C, merge presoma before obtaining graphitization, then carry out graphitization heat treatment at 3000 DEG C after, obtain the composite cathode material for lithium ion cell of coated second time shell.
Embodiment 3
With airslide disintegrating mill, isotropic coke being crushed to D50 is about 0.7 μm, the water of the isotropic coke particle of graphite granule, whole composite graphite quality 12%, the pitch of whole composite graphite quality 10% and 4L/ kilogram of graphite quality is mixed, under the rotating speed of 60r/min, mix 60min, obtain mixing emulsion; To mix emulsion in fusion machine, at the rotating speed of 600r/min, fusion temperature is merge 160min under the condition of 60 DEG C, obtains merging presoma; Under argon shield gas, fusion presoma is placed in high temperature furnace and is warming up to 800 DEG C of charing process 48h with 20 DEG C/min, be then cooled to room temperature with the cooling rate of 10 DEG C/min, the presoma material with carbon element of obtained coated ground floor shell; This presoma material with carbon element is added the resin that covering amount is 15.0% of whole composite negative pole material quality, at the rotating speed of 600r/min, fusion temperature is merge 160min under the condition of 60 DEG C, merge presoma before obtaining graphitization, then carry out graphitization heat treatment at 3100 DEG C after, obtain the composite cathode material for lithium ion cell of coated second time shell.
Embodiment 4
With nanon ball-mill, isotropic coke being milled to D50 is about 300nm, the water of the isotropic coke particle of graphite granule, whole composite graphite quality 25%, the resin of whole composite graphite quality 5% and 1L/ kilogram of graphite quality is mixed, under the rotating speed of 200r/min, mix 150min, obtain mixing emulsion; To mix emulsion in fusion machine, at the rotating speed of 2000r/min, fusion temperature is merge 180min under the condition of 100 DEG C, obtains merging presoma; Under argon shield gas, fusion presoma is placed in high temperature furnace and is warming up to 700 DEG C of charing process 30h with 30 DEG C/min, be then cooled to room temperature with the cooling rate of 8 DEG C/min, the presoma material with carbon element of obtained coated ground floor shell; This presoma material with carbon element is added the resin that covering amount is 20.0% of whole composite negative pole material quality, at the rotating speed of 2000r/min, fusion temperature is merge 30min under the condition of 70 DEG C, merge presoma before obtaining graphitization, then carry out graphitization heat treatment at 3200 DEG C after, obtain the composite cathode material for lithium ion cell of coated second time shell.
Embodiment 5
With airslide disintegrating mill, isotropic coke being crushed to D50 is about 2.0 μm, the water of the isotropic coke particle of graphite granule, whole composite graphite quality 10%, the pitch of whole composite graphite quality 3% and 0.5L/ kilogram of graphite quality is mixed, under the rotating speed of 150r/min, mix 100min, obtain mixing emulsion; To mix emulsion in fusion machine, at the rotating speed of 400r/min, fusion temperature is merge 180min under the condition of 50 DEG C, obtains merging presoma; Under argon shield gas, fusion presoma is placed in high temperature furnace and is warming up to 600 DEG C of charing process 20h with 15 DEG C/min, be then cooled to room temperature with the cooling rate of 6 DEG C/min, the presoma material with carbon element of obtained coated ground floor shell; This presoma material with carbon element is added the pitch that covering amount is 5.0% of whole composite negative pole material quality, at the rotating speed of 1200r/min, fusion temperature is merge 150min under the condition of 90 DEG C, merge presoma before obtaining graphitization, then carry out graphitization heat treatment at 2800 DEG C after, obtain the composite cathode material for lithium ion cell of coated second time shell.
Comparative example 1
The water of the pitch of graphite granule, whole composite graphite quality 10% and 1.5L/ kilogram of graphite quality is mixed, under the rotating speed of 150r/min, mixes 120min, obtain mixing emulsion; To mix emulsion in fusion machine, at the rotating speed of 1500r/min, fusion temperature is merge 60min under the condition of 80 DEG C, obtains merging presoma; Under argon shield gas, fusion presoma is placed in high temperature furnace and is warming up to 800 DEG C of charing process 48h with 5 DEG C/min, be then cooled to room temperature with the cooling rate of 5 DEG C/min, the presoma material with carbon element of obtained coated crust; The composite cathode material for lithium ion cell of coated crust is obtained after this presoma material with carbon element is carried out graphitization heat treatment at 3000 DEG C.
Comparative example 2
The water of the pitch of graphite granule, whole composite graphite quality 15% and 2L/ kilogram of graphite quality is mixed, under the rotating speed of 200r/min, mixes 180min, obtain mixing emulsion; To mix emulsion in fusion machine, at the rotating speed of 2000r/min, fusion temperature is merge 120min under the condition of 90 DEG C, obtains merging presoma; Under argon shield gas, fusion presoma is placed in high temperature furnace and is warming up to 700 DEG C of charing process 36h with 5 DEG C/min, be then cooled to room temperature with the cooling rate of 5 DEG C/min, the presoma material with carbon element of obtained coated crust; The composite cathode material for lithium ion cell of coated crust is obtained after this presoma material with carbon element is carried out graphitization heat treatment at 3200 DEG C.
Comparative example 3
Adopt the graphite cathode material that domestic combination property is best in the market.
Comparative example 4
Adopt the graphite cathode material (Japanese import) that international combination property is best in the market.
The physical and chemical index that table 1 is different embodiment and comparative example composite negative pole material and electrical property compare.
Table 1: physical and chemical index and the electrical property of different embodiment and comparative example composite negative pole material compare
| Example | Ground floor shell presoma material with carbon element specific area (m2/g) | Finished product average grain diameter D50 (μm) | Specific surface area of finished products (m2/g) | Negative plate compacted density | Reversible capacity (mAh/g) first | Initial coulomb efficiency (%) | High rate performance (15C/1C) | Cryogenic property (-20 DEG C) |
| Embodiment 1 | 20.372 | 16.321 | 1.023 | 1.69 | 365 | 95.5 | 95.6% | 88.3% |
| Embodiment 2 | 42.823 | 16.473 | 1.536 | 1.75 | 368 | 96.1 | 95.1% | 91.3% |
| Embodiment 3 | 48.689 | 16.264 | 1.129 | 1.83 | 371 | 95.3 | 95.8% | 90.3% |
| Embodiment 4 | 56.936 | 16.718 | 1.067 | 1.86 | 378 | 94.9 | 95.3% | 91.8% |
| Embodiment 5 | 12.231 | 16.528 | 1.986 | 1.78 | 363 | 95.8 | 94.3% | 89.6% |
| Comparative example 1 | — | 16.376 | 1.513 | 1.58 | 358 | 91.8 | 81.2% | 67.8% |
| Comparative example 2 | — | 16.575 | 1.382 | 1.56 | 354 | 92.6 | 82.3% | 68.3% |
| Comparative example 3 | 15.761 | 1.23 | 1.61 | 353 | 90.6 | 93.6％ | 75.3％ | |
| Comparative example 4 | 17.013 | 1.51 | 1.63 | 358 | 94.3 | 94.1% | 83.3% |
The composite negative pole material of above-mentioned 5 embodiments and 2 comparative examples tests its physical and chemical index and battery performance according to the method described above.
As can be seen from test result, the negative plate adopting composite negative pole material of the present invention and method to prepare can obtain very high gram specific capacity, reaches 350 ~ 380mAh/g, and very high compacted density, reaches 1.60 ~ 1.90g/cm3, thus obtains very high energy density; With the lithium ion battery that this negative pole is made, cycle performance is excellent, and the capacity after 500 times that circulates still maintains more than 90%; Cryogenic property is excellent especially, and under-20 DEG C of environment, 0.2C ratio of discharging is more than 80% of 23 DEG C of environment discharge capacity.
The above embodiment is only the preferred embodiment of the present invention.Should be understood that; for this area or those skilled in the relevant art; under the premise without departing from the principles of the invention, can also prepare the composite negative pole material and corresponding negative pole thereof that much meet this invention spirit, these also should be considered as belonging to protection scope of the present invention.
Claims (9)
1. a composite cathode material for lithium ion cell, it is characterized in that: structure that described composite cathode material for lithium ion cell has " kernel-double casing ", wherein kernel is the graphite granule of granularity 3.0 ~ 35.0 μm, and double casing comprises ground floor shell and second layer shell; Ground floor shell is received the isotropic coke of micron by granularity 300nm ~ 3.0 μm and to be bondd coated formation through binding agent, and total covering amount is 10.0 ~ 30.0% of whole composite negative pole material quality, obtains the presoma material with carbon element of coated ground floor shell after treatment; Then at the coated second layer shell of described presoma material with carbon element, described second layer shell is by pitch or resinae is coated is formed, and covering amount is 5.0 ~ 20.0% of whole composite negative pole material quality; Described composite cathode material for lithium ion cell is obtained after graphitization;
Wherein: described isotropic coke is as ground floor shell particles of aggregates, and the Ratio of long radius to short radius of described isotropic coke is 0.8 ~ 1.2, volatile matter is more than 10.0%, and particle size range is between μm nanometer to micron of 300nm ~ 3.0, and specific area is 8.0 ~ 60.0m
2/ g, particle surface has nano-porous structure.
2. composite cathode material for lithium ion cell according to claim 1, the binding agent of wherein said ground floor shell is resinae or pitch class binding agent.
3. composite cathode material for lithium ion cell according to claim 1, wherein said " kernel-double casing " structure is gradient-structure, and described gradient-structure is as follows: (1) described kernel specific area is 3.0 ~ 8.0m
2between/g, the specific area of described ground floor shell is 8.0 ~ 60.0m
2/ g, the specific area of described second layer shell is 0.8 ~ 3.5m
2/ g; (2) granularity of described kernel, ground floor shell and second layer shell progressively reduces successively; (3) ground floor shell beads surface has nano-porous structure.
4. composite cathode material for lithium ion cell according to claim 1, is characterized in that: described composite negative pole material gram specific capacity is 350 ~ 380mAh/g, and granularity is 3.0 ~ 55.0 μm, and tap density is 1.10 ~ 1.30g/ml, and specific area is 0.8 ~ 3.5m
2/ g, powder body compacted density is 1.70 ~ 2.30g/cm
3.
5. a preparation method for composite cathode material for lithium ion cell described in claim 1, comprises the following steps:
1) ground floor shell isotropic coke is carried out air-flow crushing or nanon ball-mill ball milling by airslide disintegrating mill, be crushed to by its grain graininess between μm nanometer to micron of 300nm ~ 3.0, obtained isotropic coke receives micron particles;
2) be the graphite granule of 3.0 ~ 35.0 μm by granularity, total covering amount is that 10.0 ~ 30.0% isotropic coke of whole composite negative pole material quality are received micron particles, resinae or pitch class binding agent and solvent and are placed in mixer with the ratio of 0.5 ~ 5.0 liter/Kg, under the rotating speed of 30 ~ 200r/min, mix 30 ~ 180min, obtain mixing emulsion;
3) will mix emulsion in fusion machine, at the rotating speed of 300 ~ 2000r/min, fusion temperature is merge 30 ~ 180min under the condition of 20 ~ 100 DEG C, obtains merging presoma;
4) under inert gas shielding, fusion presoma is placed in high temperature furnace and is warming up to 400 ~ 800 DEG C of charing process 10 ~ 48h with 5 ~ 30 DEG C/min, be then cooled to room temperature with the cooling rate of 5 ~ 30 DEG C/min, obtained specific area is 8.0 ~ 60.0m
2the presoma material with carbon element of the coated ground floor shell of/g;
5) the presoma material with carbon element of described coated ground floor shell is added the pitch or resin that covering amount is 5.0 ~ 20.0% of whole composite negative pole material quality, at the rotating speed of 300 ~ 2000r/min, fusion temperature is merge 30 ~ 180min under the condition of 20 ~ 100 DEG C, merge presoma before obtaining graphitization, then carry out graphitization heat treatment at 2800 ~ 3300 DEG C after, obtain the composite cathode material for lithium ion cell of coated second layer shell.
6. the preparation method of composite cathode material for lithium ion cell according to claim 5, is characterized in that described solvent is a kind of in water, ethanol, isopropyl alcohol, glycerol, acetone, toluene or dimethylbenzene or their mixed solvent.
7. the preparation method of composite cathode material for lithium ion cell according to claim 5, is characterized in that wherein said protection inert gas is the above-mentioned mist of nitrogen, argon gas, helium, neon or any ratio.
8. a negative electrode for lithium ion battery, is characterized in that: be coated in metal collector by mixed uniformly to composite negative pole material according to claim 1, binding agent and conductive agent material, and dry and roll-in forms.
9. negative pole according to claim 8, is characterized in that: this negative plate can obtain very high compacted density, reaches 1.60 ~ 1.90g/cm
3, thus obtain very high energy density; With the lithium ion battery that this negative pole is made, cycle performance is excellent, and the capacity after 500 times that circulates still maintains more than 90%; Low temperature performance excellent, under-20 DEG C of environment, 0.2C ratio of discharging is more than 80% of 23 DEG C of environment discharge capacity.
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| CA2820468A1 (en) | 2013-06-21 | 2014-12-21 | Hydro-Quebec | Anode including a lithium alloy for high energy batteries |
| CN105633357B (en) * | 2014-11-11 | 2019-09-17 | 东莞新能源科技有限公司 | Negative electrode active material and preparation method thereof and lithium ion secondary battery |
| CN105591109B (en) * | 2014-11-14 | 2018-03-09 | 青岛灵科新能源有限公司 | carbon material and preparation method thereof and lithium ion battery |
| CN104600313B (en) * | 2014-12-30 | 2017-09-12 | 东莞市凯金新能源科技股份有限公司 | A kind of lithium ion cell high-capacity graphite composite material and preparation method thereof |
| CN105047930B (en) * | 2015-06-08 | 2017-06-13 | 福建翔丰华新能源材料有限公司 | A kind of isotropic graphite negative material and preparation method thereof |
| CN107316983A (en) * | 2016-04-27 | 2017-11-03 | 宁波杉杉新材料科技有限公司 | A kind of lithium ion battery composite graphite negative electrode material and preparation method thereof |
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| CN108808006B (en) * | 2018-04-28 | 2020-12-11 | 宁德时代新能源科技股份有限公司 | Negative pole piece and battery |
| CN110165195A (en) * | 2019-06-13 | 2019-08-23 | 广东凯金新能源科技股份有限公司 | A kind of secondary lithium battery composite graphite particles and preparation method thereof |
| CN113451575B (en) * | 2020-03-24 | 2022-09-09 | 比亚迪股份有限公司 | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery |
| CN111554898B (en) * | 2020-05-11 | 2022-02-11 | 珠海冠宇电池股份有限公司 | Negative electrode material and preparation method and application thereof |
| CN114583119B (en) * | 2020-12-01 | 2024-02-27 | 湖南中科星城石墨有限公司 | Preparation method of composite particles, composite particles prepared by using preparation method and application of composite particles |
| CN112670471B (en) * | 2020-12-21 | 2022-02-15 | 宁波杉杉新材料科技有限公司 | Graphite negative electrode material, lithium ion battery and preparation method and application of graphite negative electrode material |
| CN112670472A (en) * | 2020-12-22 | 2021-04-16 | 宁波杉杉新材料科技有限公司 | Graphite negative electrode material, lithium ion battery, preparation method and application |
| CN112713271B (en) * | 2020-12-29 | 2022-07-05 | 上海杉杉科技有限公司 | Modified graphite material, preparation method thereof, lithium ion battery and application |
| CN114824226B (en) * | 2022-05-13 | 2023-07-14 | 欣旺达电动汽车电池有限公司 | Negative electrode plate, preparation method thereof, lithium ion battery and electric equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1909269A (en) * | 2005-08-03 | 2007-02-07 | 上海杉杉科技有限公司 | Charcoal negative electrode material and its preparation method |
| CN102030326A (en) * | 2010-11-22 | 2011-04-27 | 中科恒达石墨股份有限公司 | Preparation method of graphite cathode material |
| CN102255077A (en) * | 2010-05-21 | 2011-11-23 | 深圳市比克电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
-
2012
- 2012-11-05 CN CN201210434960.XA patent/CN102956889B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1909269A (en) * | 2005-08-03 | 2007-02-07 | 上海杉杉科技有限公司 | Charcoal negative electrode material and its preparation method |
| CN102255077A (en) * | 2010-05-21 | 2011-11-23 | 深圳市比克电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN102030326A (en) * | 2010-11-22 | 2011-04-27 | 中科恒达石墨股份有限公司 | Preparation method of graphite cathode material |
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