CN103996833A - Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material - Google Patents
Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material Download PDFInfo
- Publication number
- CN103996833A CN103996833A CN201410258525.5A CN201410258525A CN103996833A CN 103996833 A CN103996833 A CN 103996833A CN 201410258525 A CN201410258525 A CN 201410258525A CN 103996833 A CN103996833 A CN 103996833A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- preparation
- carbon microsphere
- lithium ion
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of a lithium ion battery, and particularly relates to a modified hard carbon microsphere negative material for a lithium ion battery and a preparation method of the material. The preparation method comprises the following steps: mixing potato starch which is taken as a raw material and silica sol which is taken as a catalyst according to a given ratio, drying the mixture in a vacuum drying box at the temperature of 80 to 100 DEG C, then heating a sample in a quartz tubular furnace to 800 to 1,600 DEG C under the effect of an inert atmosphere, and naturally cooling the sample to obtain the modified hard carbon microsphere negative material, wherein the specific surface area of the obtained modified hard carbon microsphere negative material is 1 m<2>/g to 100 m<2>/g, the average granularity of the modified hard carbon microsphere negative material is 60 micrometers to 80 micrometers, and the crystal surface interlayer distance d002 is 0.35 to 0.45nm. The method is simple and easy, free from environmental pollution and easy for realizing the industrialized mass production. The modified hard carbon microsphere negative material is high in reversible capacity, good in large-current charging-discharging performance and excellent in cycling performance.
Description
Technical field
The present invention relates to hard carbon microsphere cathode material of a kind of lithium ion battery modification and preparation method thereof, belong to technical field of lithium ion.
Background technology
Along with scientific and technological development, increasing electric motor car enters in people's life.And the battery overwhelming majority who is applied at present in electric motor car is lead acid accumulator, exist cycle life poor, specific energy is low, the shortcomings such as self-discharge rate height, and the lead and the sulfuric acid that produce all produce certain harm to environment thereupon, air pollution is in aggravation, and lead acid accumulator has become one of the most dangerous solid waste, and novel battery more environmental protection, that can replace lead acid accumulator is badly in need of needing to be researched and developed.
Lithium ion battery has extended cycle life because it has, and energy density is high, and specific power is high, and self discharge is little, memory-less effect, and the advantages such as non-environmental-pollution, are applied to increasing field.
Lithium ion battery negative material is mainly graphite type material in the market, its theoretical specific discharge capacity lower (372mAh/g), and under high current density condition, the charge-discharge performance of graphite type material is poor.For this reason, people are constantly studying various material with carbon elements always, are devoted to improve the high rate during charging-discharging of lithium ion battery, improve circulating battery characteristic and multiplying power property simultaneously.
Hard carbon material has underdeveloped graphite network plane, and La is less for crystallite width, and stacking number of plies Lc is less, structural arrangement disorder (d
002greatly), the storage that more emptying aperture structure is lithium provides good place, make hard charcoal have very high embedding lithium capacity, and it has good circulation and high rate performance.Therefore,, with graphite-phase ratio, hard carbon material does lithium ion battery negative material and have good fast charging and discharging performance under large electric current.
At present, research about the hard charcoal of preparation mostly relates to three major types: biomass class (as: timber, coconut husk etc.), mineral substance (as: coal, petroleum coke etc.) and synthetic polymer class (as: phenolic resins etc.), in short supply due to mineral matter resource, and the production technology of synthetic polymer and raw material sources problem, biomass class raw material have caused researchers' extensive concern because of its wide material sources, with low cost and recyclability.
Biomass class is raw-material varied, and preparation method's difference, causes the microstructure of prepared hard carbon material and the chemical property of its button half-cell of preparing also different.Patent CN102364727 is taking expanded graphite as template, hard starch base carbon microspheres is inlaid in the middle of expanded graphite space, form space conductive network, for the conduction of electronics provides good passage, the composite material discharge capacity in the time of 0.1C forming is 440～530mAh/g, and efficiency is 77～85% first, but its process is loaded down with trivial details, and cost is higher.Patent CN01817830.3, taking sucrose etc. as raw material, utilizes hydro thermal method to prepare spherical RESEARCH OF PYROCARBON, and reversible capacity is 430mAh/g, but it adopts hydro thermal method, high-temperature and high-pressure conditions, and higher to equipment requirement, security performance is poor.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of lithium ion battery modification and preparation method thereof; The method is simple, and environmental protection is easy to large-scale industrial and produces; The hard carbon microsphere cathode material specific capacity obtaining is high, can be under large electric current fast charging and discharging, high rate performance and good cycle.
The preparation method who the invention provides the hard carbon microsphere cathode material of a kind of lithium ion battery modification, comprises the following steps:
(1), taking farina as raw material, Ludox is catalyst, and farina and Ludox are mixed to get to solidliquid mixture; Wherein: the nanometer SiO in Ludox
2account for the nanometer SiO in farina and Ludox
2the 1-20% of total weight;
(2) solidliquid mixture step (1) being obtained fully stirs or ultrasonic concussion, makes to mix; In drying box, dry again, obtained flooding the starch powder of catalyst;
(3) dipping step (2) being obtained the starch powder of catalyst join in heating furnace, under inert atmosphere, rise to after 230～300 DEG C with the heating rate of 0.1～5 DEG C/min, be incubated 1～4 hour, rise to after 800～1600 DEG C with the heating rate of 1～10 DEG C/min again, be incubated 0.5～4 hour, after completing, under inert atmosphere, be cooled to room temperature, obtain the hard carbon microspheres of modification.
In above-mentioned steps (1), the mass percent concentration of described Ludox is 25%.
In above-mentioned steps (2), described stirring is to stir 10～300 minutes with rotating speed 100～1500r/min at 20～80 DEG C of temperature.
In above-mentioned steps (2), described ultrasonic concussion is at 20～40 DEG C of temperature, shakes 60～300 minutes with the power of 200～500w.
In above-mentioned steps (2), it is to dry 12～24 hours at 50～100 DEG C of temperature that described drying box is dried.
In above-mentioned steps (3), described heating furnace is tube furnace, box type furnace or converter.
In above-mentioned steps (3), described inert atmosphere is nitrogen atmosphere, argon gas atmosphere or helium atmosphere.
The present invention also provides the modification of a kind of lithium ion battery hard carbon microsphere cathode material, and the hard carbon microspheres specific area of described modification is 1～100m
2/ g, average grain particle diameter is 60～85 μ m, crystal face interlamellar spacing d
002be 0.35～0.45nm.
Useful technique effect of the present invention is:
1, the present invention uses farina for initial feed; cheap; source is abundant; and be widespread in nature; the preparation that the intrinsic spherical morphology of farina is spherical hard charcoal provides best convenient condition, has reduced special balling technique, and technique is simple; only need stabilisation, carbonation step processing, be easy to large-scale industrial and produce.
2, the present invention carries out stabilisation, carbonization treatment under inert atmosphere, has reduced the generation of impurity in sample and corrosive equipment not, easily realizes stabilisation, a step continued operation of carbonization.
3, the present invention utilizes Ludox as catalyst, effectively improves the theoretical capacity of negative material; The hard carbon microsphere cathode material specific capacity obtaining is high, can be under large electric current fast charging and discharging, high rate performance and good cycle.
Brief description of the drawings
Fig. 1 is that the raw material using in the present invention is scanning electron microscopy (SEM) figure of farina.
Fig. 2 is scanning electron microscopy (SEM) figure of the hard carbon microsphere cathode material of modification that obtains of the embodiment of the present invention 1.
Fig. 3 is X-ray diffraction (XRD) figure of the hard carbon microsphere cathode material of modification that obtains of the embodiment of the present invention 1.
Fig. 4 is the first all charging and discharging curves of 0.1C of the button half-cell of the hard carbon microsphere cathode material of modification that obtains of embodiment 1, and current density is 60mA/g.
Fig. 5 is the curve of the high rate performance (0.1C, 0.5C, 1C, 2C, 3C, 5C, 10C) of the hard carbon microsphere cathode material button of the modification half-cell that obtains of embodiment 1.
Fig. 6 is the 5C cycle performance curve of the button half-cell of the hard carbon microsphere cathode material of modification that obtains of embodiment 1, and current density is 3000mA/g.
Embodiment
The present invention adopts the Japanese HITACHI S-4800 of company type scanning electron microscopy (SEM), and accelerating voltage 5.0kV～10.0kV carries out morphology characterization to farina and the hard carbon microsphere cathode material of lithium ion battery modification obtaining.
The present invention adopts the German Brooker AXS of company (Bruker-AXS) D8 ADVANCE DiffractometerX x ray diffractometer x (CuK-Alpha, λ=0.15406nm), tube current 40mA, tube voltage 40KV, 0.02 ° of scanning step, carries out crystal structure detection to the lithium ion battery obtaining with the hard carbon microsphere cathode material of modification.
The present invention is as follows for making the concrete grammar of button half-cell by hard modification carbon microsphere cathode material:
Hard modification carbon microsphere cathode material is fully uniformly mixed with the mass ratio of 91.6:6.6:1.8 with PVDF and conductive black respectively, then the negative electrode component material stirring is evenly spread upon on the one side of Copper Foil, put into 85 DEG C of vacuum drying chambers dry, the disk that is washed into diameter 16 mm after roll-in is stand-by; Positive electricity very can lithium industry metal lithium sheet in Tianjin, and diaphragm is U.S. CE LGARD3501, the LiPFB that electrolyte is 1mol/L
6BdMC+EMC+PC (3:2:5)+VC1%), be less than 2% in relative humidity, in the glove box of logical argon gas, make button cell, after assembling, after standing 12-24h, carry out electrochemical property test.
In the present invention, electrochemical property test adopts Wuhan Land CT-2001A type automatic inflatable electric tester prepared button cell to be carried out to charge-discharge test, testing range 5V/100mA.
In the present invention, first discharge specific capacity and initial charge specific capacity are to be discharged to first the discharge capacity of 0.005V and the ratio of active material quality and the ratio to charging capacity and the active material quality of 2V with 0.1C electric current initial charge with 0.1C electric current.
In the present invention, first charge-discharge efficiency, coulomb efficiency is charging capacity and first discharge capacity percent value first first.
In the present invention, cycle performance testing procedure is: with the current charges of 5C to 2V, then with the current discharge of 0.1C to 0.005V.
In the present invention, high rate performance testing procedure is: successively with the current charges of 0.1C to 2V, the current discharge of 0.1C is to 0.005V; The current charges of 0.5C is to 2V, and the current discharge of 0.1C is to 0.005V; The current charges of 1C is to 2V, and the current discharge of 0.1C is to 0.005V; The current charges of 2C is to 2V, and the current discharge of 0.1C is to 0.005V; The current discharge of 3C is to 0.005V, and the current discharge of 0.1C is to 0.005V; The current charges of 5C is to 2V, and the current discharge of 0.1C is to 0.005V; The current charges of 10C is to 2V, and the current discharge of 0.1C is to 0.005V.
Further illustrate the present invention below in conjunction with instantiation, embodiments of the invention are only used for technical scheme of the present invention is described, the present invention is not limited.
Embodiment 1
The hard carbon microsphere cathode material preparation method of a kind of modification lithium-ion battery, step comprises:
Step 1, take farina (biochemical reagents BR is purchased from Chemical Reagent Co., Ltd., Sinopharm Group) 99g, add 50-100ml deionized water, be uniformly mixed formation starch solution.
Step 2, take 4g Ludox (purchased from Qingdao Marine Chemical Co., Ltd.) (mass fraction is 25%) for catalyst (account for sample total amount 1%), add in the starch solution obtaining in step 1, form the mixture of Ludox and starch;
Step 3, the mixture that step 2 is obtained carry out stir process, and mixing time is 2h, and mixing speed is 1000 revs/min, and then carry out ultrasonic wave processing, and the processing time is 1 hour, and starch is fully mixed with Ludox;
Step 4, mixture that step 3 is obtained filter and obtain solid mixture and be placed in drying box and be dried processing, 100 DEG C of baking temperatures, and processing time 24h, has obtained flooding the starch powder of catalyst Ludox;
Step 5, put into quartz tube furnace by drying starch powder in step 4, under nitrogen atmosphere, rise to 280 DEG C with the heating rate of 2 DEG C/min, be incubated 4 hours, then rise 1200 DEG C with the heating rate of 4 DEG C/min, be incubated 2 hours, after completing, under inert atmosphere, be cooled to room temperature, obtain the hard carbon microspheres 21.37g of starch base, called after PSC-Si-001.
Hard the farina base of preparation carbon microspheres 13.40g is fully uniformly mixed as negative material using the mass ratio of 91.6:6.6:1.8 with PVDF and conductive black respectively, and lithium sheet is positive electrode, adopts the LiPFB of 1mol/L
6BdMC+EMC+PC (3:2:5)+VC1% is electrolyte, prepares button half-cell.After static 24h, in Wuhan, Land CT-2001A type automatic inflatable electric tester carries out electrochemical property test.
The present embodiment gained sample be respectively SEM photo under 1K and 3K as shown in Figure 2 in multiplication factor, can observe from this SEM figure, the farina pyrolytic hard carbon material pattern of making through above-mentioned preparation method, taking oval particle as main, has utilized the primary morphology of potato starch particle preferably.
The present embodiment gained sample carries out specific area and testing graininess, test result: BET specific area=84.2m
2/ g, D
50=68.2 μ m.
The X ray diffracting spectrum of the present embodiment as shown in Figure 3, d
002=0.3874nm.
As shown in Figure 4, charging and discharging currents density is 60mA/g to the first all charging and discharging curves of the present embodiment gained sample 0.1C, and its initial charge gram volume is 265.97mAh/g, and the gram volume that discharges is first 410.97mAh/g, and coulomb efficiency is 64.72% first.
As shown in Figure 5, under 10C current density, its electric discharge gram volume also has 209.65mAh/g to the present embodiment high rate performance, and capability retention is 51.01%; Charging gram volume also has 192.62mAh/g, and capability retention is 72.42%.
As shown in Figure 6, under 5C current density, the electric discharge gram volume circulating 100 times time also has 203.67mAh/g to the present embodiment cycle performance, and capability retention is 49.56%.
Embodiment 2
The present embodiment is identical with the step of embodiment 1, and difference is that the farina amount taking is 95g, and the Ludox amount adding is 20g, accounts for 5% of sample total amount; In step 5, first rise to 300 DEG C with the heating rate of 5 DEG C/min, be incubated 1 hour, then rise 1600 DEG C with the heating rate of 10 DEG C/min, be incubated 0.5 hour; The farina base RESEARCH OF PYROCARBON microballoon called after PSC-Si-005 obtaining, prepares farina base RESEARCH OF PYROCARBON microballoon and the material list electrochemical property test of seeking peace according to method described in embodiment 1 step.BET specific area=59.6m in the present embodiment
2/ g, D
50=77.3 μ m, d
002=0.3942nm, the first Zhou Fang electricity gram volume of 0.1C is 482.73mAh/g, and first week charging gram volume is 272.58mAh/g, and coulomb efficiency is 56.47% first; Under 10C current density, its electric discharge gram volume also has 232.83mAh/g, and capability retention is 48.23%, and its charging gram volume is 194.78 mAh/g, and capability retention is 71.46%; Under 5C current density, the electric discharge gram volume 149.88mAh/g circulating 100 times time, capability retention is 31.05%.
Embodiment 3
The present embodiment is identical with the step of embodiment 1, difference is that the farina amount taking is 90g, the Ludox amount adding is 40g, account for 10% of sample total amount, in step 5, first rise to 230 DEG C with the heating rate of 0.1 DEG C/min, be incubated 4 hours, rise 800 DEG C with the heating rate of 1 DEG C/min again, be incubated 4 hours; The farina base RESEARCH OF PYROCARBON microballoon called after PSC-Si-010 obtaining, prepares farina base RESEARCH OF PYROCARBON microballoon and the material list electrochemical property test of seeking peace according to method described in embodiment 1 step.BET specific area=26.4m in the present embodiment
2/ g, D
50=78.9 μ m, d
002=0.3921nm, the first Zhou Fang electricity gram volume of 0.1C is 565.42mAh/g, and first week charging gram volume is 304.21mAh/g, and coulomb efficiency is 53.80% first; Under 10C current density, its electric discharge gram volume also has 241.29mAh/g, and capability retention is 42.67%, and its charging gram volume is 212.47 mAh/g, and capability retention is 69.84%; Under 5C current density, the electric discharge gram volume 258.35mAh/g circulating 100 times time, capability retention is 45.69%.
Embodiment 4
The present embodiment is identical with the step of embodiment 1, difference is that the farina amount taking is 85g, the Ludox amount adding is 60g, account for 15% of sample total amount, called after PSC-Si-015, prepares farina base RESEARCH OF PYROCARBON microballoon and the material list electrochemical property test of seeking peace according to method described in embodiment 1 step.BET specific area=14.2m in the present embodiment
2/ g, D
50=80.8 μ m, d
002=0.3856nm, the first Zhou Fang electricity gram volume of 0.1C is 623.82mAh/g, and first week charging gram volume is 345.38mAh/g, and coulomb efficiency is 55.37% first; Under 10C current density, its electric discharge gram volume also has 357.34mAh/g, and capability retention is 57.28%, and its charging gram volume is 233.44mAh/g, and capability retention is 67.59%; Under 5C current density, the electric discharge gram volume 262.19mAh/g circulating 100 times time, capability retention is 42.03%.
Embodiment 5
The present embodiment is identical with the step of embodiment 1, difference is that the farina amount taking is 80g, the Ludox amount adding is 80g, account for 20% of sample total amount, called after PSC-Si-020, prepares farina base RESEARCH OF PYROCARBON microballoon and the material list electrochemical property test of seeking peace according to method described in embodiment 1 step.BET specific area=2.8m in the present embodiment
2/ g, D
50=84.5 μ m, d
002=0.3869nm, the first Zhou Fang electricity gram volume of 0.1C is 659.47mAh/g, and first week charging gram volume is 357.92mAh/g, and coulomb efficiency is 54.27% first; Under 10C current density, its electric discharge gram volume also has 309.51mAh/g, and capability retention is 46.93%, and its charging gram volume is 278.91mAh/g, and capability retention is 77.93%; Under 5C current density, the electric discharge gram volume 232.73mAh/g circulating 100 times time, capability retention is 42.03%.
Comparative example
Comparative example is identical with the step of embodiment 1, difference is that the farina amount taking is 100g, do not add Ludox, called after PSC-Si-000, prepares farina base RESEARCH OF PYROCARBON microballoon and the material list electrochemical property test of seeking peace according to method described in embodiment 1 step.BET specific area=128.6m in the present embodiment
2/ g, D
50=82.5 μ m, d
002=0.3992nm, the first Zhou Fang electricity gram volume of 0.1C is 645.46mAh/g, and first week charging gram volume is 220.91mAh/g, and coulomb efficiency is 34.23% first; Under 10C current density, its electric discharge gram volume also has 218.24mAh/g, and capability retention is 33.81%, and its charging gram volume is 68.00 mAh/g, and capability retention is 30.78%; Under 5C current density, the electric discharge gram volume 191.83mAh/g circulating 100 times time, capability retention is 29.72%.
Can find out from comparative example, the hard carbon microspheres of farina base prepared by the method for the invention, pattern is elliposoidal, and the battery efficiency of preparation is high, and high rate performance and good cycle are obviously better than comparison example.Can realize the requirement of lithium ion battery fast charging and discharging under large electric current.
Table 1 is the electrical performance data of farina base RESEARCH OF PYROCARBON material in the embodiment of the present invention.
。
Claims (9)
1. a preparation method for the hard carbon microsphere cathode material of modification for lithium ion battery, is characterized in that comprising the following steps:
(1), taking farina as raw material, Ludox is catalyst, and farina and Ludox are mixed to get to solidliquid mixture; Wherein: the nanometer SiO in Ludox
2account for the nanometer SiO in farina and Ludox
21～20% of total weight;
(2) solidliquid mixture step (1) being obtained fully stirs or ultrasonic concussion, makes to mix; In drying box, dry again, obtained flooding the starch powder of catalyst;
(3) dipping step (2) being obtained the starch powder of catalyst join in heating furnace, under inert atmosphere, rise to after 230～300 DEG C with the heating rate of 0.1～5 DEG C/min, be incubated 1～4 hour, rise to after 800～1600 DEG C with the heating rate of 1～10 DEG C/min again, be incubated 0.5～4 hour, after completing, under inert atmosphere, be cooled to room temperature, obtain the hard carbon microspheres of modification.
2. preparation method according to claim 1, is characterized in that: in step (1), the mass percent concentration of described Ludox is 25%.
3. preparation method according to claim 1, is characterized in that: in step (2), described stirring is to stir 10～300 minutes with rotating speed 100～1500r/min at 20～80 DEG C of temperature.
4. preparation method according to claim 1, is characterized in that: in step (2), described ultrasonic concussion is at 20～40 DEG C of temperature, shakes 60～300 minutes with the power of 200～500w.
5. preparation method according to claim 1, is characterized in that: in step (2), it is to dry 12～24 hours at 50～100 DEG C of temperature that described drying box is dried.
6. preparation method according to claim 1, is characterized in that: in step (3), described heating furnace is tube furnace, box type furnace or converter.
7. preparation method according to claim 1, is characterized in that: in step (3), described inert atmosphere is nitrogen atmosphere, argon gas atmosphere or helium atmosphere.
8. the hard carbon microsphere cathode material of lithium ion battery modification obtaining according to the preparation method one of claim 1-7 Suo Shu, is characterized in that: the hard carbon microspheres specific area of described modification is 1～100m
2/ g, average grain particle diameter is 60～85 μ m, crystal face interlamellar spacing d
002be 0.35～0.45nm.
9. the hard carbon microsphere cathode material of modification for lithium ion battery according to claim 8, is characterized in that: the hard carbon microspheres specific area of described modification is 2.8～84.2m
2/ g, average grain particle diameter is 68.2～84.5 μ m, crystal face interlamellar spacing d
002for 0.3856-0.3942nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410258525.5A CN103996833A (en) | 2014-06-12 | 2014-06-12 | Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410258525.5A CN103996833A (en) | 2014-06-12 | 2014-06-12 | Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103996833A true CN103996833A (en) | 2014-08-20 |
Family
ID=51310918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410258525.5A Pending CN103996833A (en) | 2014-06-12 | 2014-06-12 | Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103996833A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109686975A (en) * | 2018-12-05 | 2019-04-26 | 桑德集团有限公司 | A kind of hard charcoal negative electrode material and preparation method thereof |
| CN109860594A (en) * | 2019-01-18 | 2019-06-07 | 三峡大学 | A kind of preparation method of starch residue preparation negative electrode material |
| CN112777591A (en) * | 2021-01-15 | 2021-05-11 | 无锡东恒新能源科技有限公司 | Preparation method of lithium battery negative electrode material |
| WO2021116455A1 (en) * | 2019-12-13 | 2021-06-17 | Centre National De La Recherche Scientifique | Carbon material, use thereof in batteries, method for producing said material and electrode comprising same |
| CN114873579A (en) * | 2022-05-10 | 2022-08-09 | 山东能源集团有限公司 | Composite carbon microsphere, preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717072A (en) * | 2009-12-07 | 2010-06-02 | 北京化工大学 | Method for storing hydrogen and carbon dioxide by active carbon microballoons |
| CN101717085A (en) * | 2009-12-07 | 2010-06-02 | 北京化工大学 | Activated carbon microspheres and preparation method thereof |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN102364727A (en) * | 2011-11-15 | 2012-02-29 | 中国东方电气集团有限公司 | Hard carbon micro-spherical composite anode material of lithium battery and preparation method for hard carbon micro-spherical composite anode material |
| CN103022452A (en) * | 2013-01-08 | 2013-04-03 | 天津大学 | Preparation method of graphitic microspheres for lithium ion battery negative electrode |
| CN103420358A (en) * | 2013-08-02 | 2013-12-04 | 鲁南煤化工研究院 | Method for preparing mesocarbon microbeads |
| CN103569995A (en) * | 2012-07-30 | 2014-02-12 | 中国科学院兰州化学物理研究所 | Preparation method of porous carbon microsphere |
-
2014
- 2014-06-12 CN CN201410258525.5A patent/CN103996833A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717072A (en) * | 2009-12-07 | 2010-06-02 | 北京化工大学 | Method for storing hydrogen and carbon dioxide by active carbon microballoons |
| CN101717085A (en) * | 2009-12-07 | 2010-06-02 | 北京化工大学 | Activated carbon microspheres and preparation method thereof |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN102364727A (en) * | 2011-11-15 | 2012-02-29 | 中国东方电气集团有限公司 | Hard carbon micro-spherical composite anode material of lithium battery and preparation method for hard carbon micro-spherical composite anode material |
| CN103569995A (en) * | 2012-07-30 | 2014-02-12 | 中国科学院兰州化学物理研究所 | Preparation method of porous carbon microsphere |
| CN103022452A (en) * | 2013-01-08 | 2013-04-03 | 天津大学 | Preparation method of graphitic microspheres for lithium ion battery negative electrode |
| CN103420358A (en) * | 2013-08-02 | 2013-12-04 | 鲁南煤化工研究院 | Method for preparing mesocarbon microbeads |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109686975A (en) * | 2018-12-05 | 2019-04-26 | 桑德集团有限公司 | A kind of hard charcoal negative electrode material and preparation method thereof |
| CN109860594A (en) * | 2019-01-18 | 2019-06-07 | 三峡大学 | A kind of preparation method of starch residue preparation negative electrode material |
| CN109860594B (en) * | 2019-01-18 | 2021-08-24 | 三峡大学 | Preparation method for preparing negative electrode material from starch residues |
| WO2021116455A1 (en) * | 2019-12-13 | 2021-06-17 | Centre National De La Recherche Scientifique | Carbon material, use thereof in batteries, method for producing said material and electrode comprising same |
| FR3104565A1 (en) * | 2019-12-13 | 2021-06-18 | Centre National De La Recherche Scientifique | Carbonaceous material, its use in batteries, its manufacturing process and an electrode comprising it |
| CN115279689A (en) * | 2019-12-13 | 2022-11-01 | 法国国家科研中心 | Carbon material, use thereof in a battery, method for producing said material and electrode comprising said material |
| CN112777591A (en) * | 2021-01-15 | 2021-05-11 | 无锡东恒新能源科技有限公司 | Preparation method of lithium battery negative electrode material |
| CN112777591B (en) * | 2021-01-15 | 2022-02-22 | 无锡东恒新能源科技有限公司 | Preparation method of lithium battery negative electrode material |
| CN114873579A (en) * | 2022-05-10 | 2022-08-09 | 山东能源集团有限公司 | Composite carbon microsphere, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104009210B (en) | A kind of porous silicon/carbon composite material, Preparation method and use | |
| CN108059144B (en) | Hard carbon prepared from biomass waste bagasse, and preparation method and application thereof | |
| CN107611411B (en) | Preparation method and application of three-dimensional hierarchical porous nitrogen-doped carbon-coated silicon composite material | |
| CN113113602B (en) | Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof | |
| CN105098186A (en) | Pyrolysis amorphous carbon material and preparation method and application thereof | |
| CN109921020A (en) | A kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material | |
| CN107946568B (en) | High-performance silicon oxide/hard carbon/graphite composite material and preparation method and application thereof | |
| CN103840161A (en) | Method for preparing lithium battery negative electrode material, and lithium battery negative electrode sheet | |
| CN104009235A (en) | Preparation method of porous silicon/graphene composite material | |
| CN103996833A (en) | Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN112110448A (en) | Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof | |
| CN104377346B (en) | Method for preparing modified graphite negative electrode material of sodium ion battery | |
| CN109616645A (en) | A kind of flexible silicium cathode and preparation method thereof for lithium ion battery | |
| CN108615888B (en) | Biomass carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof | |
| CN104966814A (en) | High-security metallic lithium cathode and preparation method thereof | |
| CN112736232A (en) | Silicon-carbon composite material, preparation method thereof, negative plate and lithium ion secondary battery | |
| CN113889594A (en) | Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material | |
| CN111313012A (en) | Multiwalled carbon nanotube graphite lithium ion battery negative electrode material and preparation method thereof | |
| CN103311518B (en) | Hard-carbon negative electrode material for lithium ion secondary battery and preparation method thereof | |
| CN107611378A (en) | Nitrogen-containing composite material for zinc-based battery and preparation method thereof | |
| CN106684367B (en) | Low-temperature petroleum coke negative electrode material coated with nitrogen-containing polymer pyrolytic carbon and preparation method thereof | |
| CN110474051A (en) | A kind of application of common dyes rhodamine B as the organic positive electrode of lithium ion battery | |
| Yuan et al. | Facile synthesis of SiO2/C composite and its application as anode material for lithium ion batde | |
| CN115249799A (en) | Rosin-based nitrogen-doped coated hard carbon negative electrode material of sodium ion battery and preparation method of rosin-based nitrogen-doped coated hard carbon negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140820 |
|
| WD01 | Invention patent application deemed withdrawn after publication |