CN104445146B - A kind of production method of power lithium-ion battery Graphene Modified Activated Carbon negative material - Google Patents
A kind of production method of power lithium-ion battery Graphene Modified Activated Carbon negative material Download PDFInfo
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- CN104445146B CN104445146B CN201410666062.6A CN201410666062A CN104445146B CN 104445146 B CN104445146 B CN 104445146B CN 201410666062 A CN201410666062 A CN 201410666062A CN 104445146 B CN104445146 B CN 104445146B
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Abstract
The invention provides a kind of production method of power lithium-ion battery Graphene Modified Activated Carbon negative material, take mesophase pitch as raw material A, be that modifier B carries out modification again with Graphene, A, B bis-kinds of raw materials carry out mixed at high speed by certain weight ratio, incorporation time 2-5 hour, obtain material C, material C is carried out oxidation processes at 200 ~ 260 DEG C of temperature, oxidization time is 3h ~ 5h, then material D is obtained, with lithium battery solvent for the material D lithium battery solvent after oxidation processes is carried out the process of liquid phase mix and blend by certain volume ratio by raw material E, spraying dry balling-up is carried out at 500 ~ 1300 DEG C, at 2400 ~ 3200 DEG C of temperature, graphitization processing is carried out after spheroidising, the reddest graphited material to be sieved, packaging, finally obtain product of the present invention.The invention has the advantages that: cryogenic property is good, stable cycle performance.
Description
Technical field
The present invention relates to a kind of manufacture method of power lithium-ion battery Graphene Modified Activated Carbon negative material, belong to technical field of lithium ion battery negative.
Background technology
Apply more and more widely along with lithium ion battery obtains, especially obtain in the application in electric automobile field and approve widely, from now on may longer one period automobile demand amount will keep growth, for avoiding the nervous and problem of environmental pollution of the resource brought thus, accelerate Promoting Industrial transition and upgrade, recent State Council and each ministries and commissions, local government is intensive has put into effect relevant behave, tries hard to recommend the accelerated development of New Energy Sources In China automobile and popularization.July in this year, the General Office of the State Council prints and distributes " instruction about quickening new-energy automobile is applied ", and soon subsequently, relevant ministries and commissions once again hereafter, explicitly call for the ratio of the new-energy automobile that central authorities, each place government bodies and public organizations buy, and improved year by year.Chinese Government, in " energy-conservation with new-energy automobile industrial development planning (2012-2020) " that passed through last year, determines the year two thousand twenty, and pure electric automobile and plug-in hybrid-power automobile production capacity reach 2,000,000, accumulative volume of production and marketing crosses 5,000,000.
At present, combination property can meet electric automobile requirement, and the electrokinetic cell that technology is the most ripe only has lithium ion battery.Benefit from the double drive in policy and market, lithium battery industry obtains develop rapidly.Within 2014,1-6 month Electric Cars in China sales volume is 2.06 ten thousand, increases by 220% on a year-on-year basis, and the same period, the output of electrokinetic cell was 1.18GWH, increased by 23.2% on a year-on-year basis.There is mechanism to predict, be expected to realize the marketization completely to the year two thousand twenty new-energy automobile market.
In actual applications, lithium ion battery negative material remains occupies an leading position with graphite type material, its as power negative material not only stable circulation performance have much room for improvement, low temperature performance is also its deadly defect.Usually the surface of negative material adopt coated, modification improves its capacity, improve its cycle performance, although there is certain effect, but effect is not also too obvious, as: JP2000357506 carries out coated with cracking graphite to charcoal or graphite powder, adopt this coating modification method can not obtain the coating layer of even compact, and coating layer is thicker, the processing characteristics of graphite and stable circulation performance are all had a certain impact.CN96198348 first floods graphite with mink cell focus, and then carry out coating modification, although the more direct covered effect of this method is much better, the electric conductivity of powder does not get a promotion, on the contrary, capacity and processing characteristics also can have a certain impact.
Summary of the invention
The object of this invention is to provide a kind of production method of power lithium-ion battery Graphene Modified Activated Carbon negative material, the method is produced lithium ion battery negative material and is had features such as promoting stable circulation performance, low temperature performance and expansion capacity.
Technical scheme of the present invention: a kind of production method of power lithium-ion battery Graphene Modified Activated Carbon negative material, concrete production technology is:
A raw material A for raw material A, is first carried out mechanical crushing with petroleum asphalt, coal tar pitch or mesophase pitch by (), then will shatter the particle nanometer obtained, the particle diameter D of described raw material A
50between 50 ~ 600nm; Described petroleum asphalt is petroleum by-product, and namely described petroleum asphalt is residue, mid temperature pitch after crude distillation; Described coal tar pitch is High softening-point modified pitch, pitch; Described mesophase pitch is mesophase ball modified coal tar pitch;
B () take Graphene as modifier B, modifier B is carried out mechanical crushing, then will shatter the particle nanometer obtained, the particle diameter D of described modifier B
50between 5 ~ 100nm, Graphene is single-layer graphene film or multi-layer graphene powder;
(c) by above-described A, B bis-kinds of raw materials by weight A/B=(80 ~ 95)/(5 ~ 20) carry out mixed at high speed, speed is 800-3000 rev/min, incorporation time 2-5 hour, obtains material C;
D material C is carried out oxidation processes by () at 200 ~ 260 DEG C of temperature, oxidization time is 3h ~ 5h, then obtains material D;
E (), with lithium battery solvent for raw material E, described solvent is oiliness or water-based, namely lithium battery solvent is that PVDF adds NMP oleaginous system, or lithium battery solvent is CMC water-based system;
F () is by material D and raw material E D/E=(30 ~ 50 by volume)/(60 ~ 100) carry out mix and blend, stirring can adopt the agitating mode of screw rod or taper mixing, mixing time 1-5 hour, then at 500 ~ 1300 DEG C, carry out spraying dry balling-up by employing spraying dry balling-up equipment, described spraying dry balling-up equipment is hig h-speed centrifugal spray drying balling-up equipment or high-boiling spraying dry balling-up equipment;
G material that step (f) obtains by () carries out graphitization processing at 2400 ~ 3200 DEG C of temperature;
H graphited material that step (g) finally obtains by () carries out sieving, packing, and obtains product of the present invention.
Beneficial effect of the present invention:
1, the present invention adopts nano material to make raw material, not only makes the absorbent of micron particles be fundamentally improved, and also assures that the stable circulation performance of material simultaneously;
2, adopt Graphene to be modifier, substantially increase the electric conductivity of graphite granule, extend cycle life and the low-temperature circulating life-span of Modified Activated Carbon material;
3, carbon cathode material of the present invention adopts nano oxidized, graphitization and spheroidizing process in process of production, and operation is comparatively simple, and production efficiency is high, and material property is very stable; Compared with prior art, spheroidizing process adopts spraying dry ball, and nodularization effect is good, even particle size distribution, and jolt ramming is high.
4, the present invention adopts the advantage of lithium ion battery oiliness or aqueous solvent to be not introduce the foreign matter that to have nothing to do with lithium battery, also ensures the stability of material.
Embodiment
embodiment 1:
Get the mesophase pitch of 500 grams, carried out mechanical crushing to D
50be about 20um, then by micro particles nanometer, it controls particle diameter D
50be about 80nm, it is designated as raw material A; Then be the particle diameter D of modifier B, described modifier B with graphene film
50for 10nm; A, B are carried out mixed at high speed by weight A/B=95/5 high speed cone-type mixer, and incorporation time is 2 hours, obtains material C; Again material C is carried out oxidation processes at 250 DEG C of temperature, oxidization time is 3 hours, then obtains material D; Add NMP oleaginous system with PVDF to be designated as raw material E and to prepare burden, D/E=1/3 carries out mix and blend by volume, and mixing time 5 hours, then carries out spraying dry balling-up, i.e. spheroidising at 550 DEG C; Graphitization processing is carried out again at 3000 DEG C of temperature; Finally graphited material is carried out sieving, packing, finally obtain product of the present invention.
Do experiment with button cell, gained negative material first discharge capacity is 355.8mAh/g, and discharging efficiency is 94.2% first.With 0.1C charge and discharge, after 100 circulations, capacity keeps 98.2%; After 300 circulations, capacity keeps 95.1%; After 500 circulations, capacity keeps 93.5%.
embodiment 2:
Get the petroleum asphalt of 600 grams, carried out mechanical crushing to D
50be about 26um, then by its particle nanometer, it controls particle diameter D
50be about 150nm, it is designated as raw material A; Then be the particle diameter D of modifier B, described modifier B with Graphene
50for 20nm; A, B are carried out mixed at high speed by weight A/B=92/8 high speed cone-type mixer, and incorporation time is 3 hours, obtains material C; Again material C is carried out oxidation processes at 220 DEG C of temperature, oxidization time is 2 hours, then obtains material D; Be designated as raw material E with CMC water-based system to prepare burden, D/E=2/3 carries out mix and blend by volume, and mixing time 4.5 hours, then carries out spraying dry balling-up at 1200 DEG C; At 2450 DEG C of temperature, carry out graphitization processing again, finally graphited material is carried out sieving, packing, finally obtain product of the present invention.
Do experiment with button cell, gained negative material first discharge capacity is 352.9mAh/g, and discharging efficiency is 94.8% first.With 0.1C charge and discharge, after 100 circulations, capacity keeps 97.8%; After 300 circulations, capacity keeps 93.5%; After 500 circulations, capacity keeps 92.7%.
embodiment 3:
Get the coal tar pitch of 800 grams, carried out mechanical crushing to D
50be about 30um, then by its particle nanometer, it controls particle diameter D
50be about 50nm, it is designated as raw material A; Then be the particle diameter D of raw material agent B, described modifier B with Graphene
50for 80nm; A, B are carried out mixed at high speed by weight A/B=90/1 high speed cone-type mixer, and incorporation time is 2.5 hours, obtains material C; Again material C is carried out oxidation processes at 230 DEG C of temperature, oxidization time is 1.5 hours, then obtains material D; Add NMP oleaginous system with PVDF to be designated as raw material E and to prepare burden, D/E=3/10 carries out mix and blend by volume, and mixing time 3 hours, then carries out spraying dry balling-up at 900 DEG C; At 3100 DEG C of temperature, carry out graphitization processing again, finally graphited material is carried out sieving, packing, finally obtain product of the present invention.
Do experiment with button cell, gained negative material first discharge capacity is 358.7mAh/g, and discharging efficiency is 94.5% first.With 0.1C charge and discharge, after 100 circulations, capacity keeps 98.1%; After 300 circulations, capacity keeps 95.6%; After 500 circulations, capacity keeps 93.9%.
embodiment 4:
Get the mesophase pitch of 500 grams, carried out mechanical crushing to D
50be about 15um, then by its particle nanometer, it controls particle diameter D
50be about 280nm, it is designated as raw material A; Then be the particle diameter D of modifier B, described modifier B with multi-layer graphene
50for 100nm; A, B are carried out mixed at high speed by weight A/B=95/5 high speed cone-type mixer, and incorporation time is 1 hour, obtains material C; Again material C is carried out oxidation processes at 240 DEG C of temperature, oxidization time is 1 hour, then obtains material D; Under with embodiment 1.
Do experiment with button cell, gained negative material first discharge capacity is 349.2mAh/g, and discharging efficiency is 93.8% first.With 0.1C charge and discharge, after 100 circulations, capacity keeps 95.1%; After 300 circulations, capacity keeps 91.6%; After 500 circulations, capacity keeps 88.7%.
embodiment 5:
Get the mesophase pitch of 750 grams, carried out mechanical crushing to D
50be about 18um, then by its particle nanometer, it controls particle diameter D
50be about 350nm, it is designated as raw material A; Then be the particle diameter D of modifier B, described modifier B with multi-layer graphene
50for 50nm; A, B are carried out mixed at high speed by weight A/B=96/4 high speed cone-type mixer, and incorporation time is 2 hours, obtains material C; Again material C is carried out oxidation processes at 200 DEG C of temperature, oxidization time is 1.5 hours, then obtains material D; Under with embodiment 2.
Do experiment with button cell, gained negative material first discharge capacity is 345.4mAh/g, and discharging efficiency is 93.5% first.With 0.1C charge and discharge, after 100 circulations, capacity keeps 94.8%; After 300 circulations, capacity keeps 89.5%; After 500 circulations, capacity keeps 83.6%.
embodiment 6:
Get the petroleum asphalt of 500 grams, carried out mechanical crushing to D
50be about 15um, then by its particle nanometer, it controls particle diameter D
50be about 600nm, it is designated as raw material A; Then be the particle diameter D of modifier B, described modifier B with Graphene
50for 10nm; A, B are carried out mixed at high speed by weight A/B=80/20 high speed cone-type mixer, and incorporation time is 3.5 hours, obtains material C; Again material C is carried out oxidation processes at 250 DEG C of temperature, oxidization time is 2.5 hours, then obtains material D; Under with embodiment 3.
Do experiment with button cell, gained negative material first discharge capacity is 354.5mAh/g, and discharging efficiency is 94.0% first.With 0.1C charge and discharge, after 100 circulations, capacity keeps 97.9%; After 300 circulations, capacity keeps 95.3%; After 500 circulations, capacity keeps 92.9%.
Claims (4)
1. a power lithium-ion battery production method for Graphene Modified Activated Carbon negative material, is characterized in that: concrete production technology is:
(a) with petroleum asphalt, coal tar pitch or mesophase pitch for raw material A, the particle diameter D of described raw material A
50between 50 ~ 600nm;
B () take Graphene as modifier B, the particle diameter D of described modifier B
50between 5 ~ 100nm;
(c) by above-described A, B bis-kinds of raw materials by weight A/B=(80 ~ 95)/(5 ~ 20) mix, incorporation time 2-5 hour, obtains material C;
D material C is carried out oxidation processes by () at 200 ~ 260 DEG C of temperature, oxidization time is 3h ~ 5h, then obtains material D;
E (), with lithium battery solvent for raw material E, described solvent is oiliness or water-based, namely lithium battery solvent is that PVDF adds NMP oleaginous system, or lithium battery solvent is CMC water-based system;
F () is by material D and raw material E D/E=(30 ~ 50 by volume)/(60 ~ 100) carry out mix and blend, mixing time 1-5 hour, then at 500 ~ 1300 DEG C by adopting spraying dry balling-up equipment to carry out spraying dry balling-up;
G material that step (f) obtains by () carries out graphitization processing at 2400 ~ 3200 DEG C of temperature;
H graphited material that step (g) finally obtains by () carries out sieving, packing, and obtains final products.
2. the production method of a kind of power lithium-ion battery Graphene Modified Activated Carbon negative material as claimed in claim 1, is characterized in that: described Graphene is single-layer graphene film or multi-layer graphene powder.
3. the production method of a kind of power lithium-ion battery Graphene Modified Activated Carbon negative material as claimed in claim 1, is characterized in that: described spraying dry balling-up equipment is hig h-speed centrifugal spray drying balling-up equipment or high-boiling spraying dry balling-up equipment.
4. the production method of a kind of power lithium-ion battery Graphene Modified Activated Carbon negative material as claimed in claim 1, it is characterized in that: raw material A and modifier B are through nanoparticulate process respectively, namely first carry out mechanical crushing, then will shatter the particle nanometer obtained.
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| CN104779396B (en) * | 2015-04-22 | 2017-01-11 | 大连宏光锂业股份有限公司 | Production method of lithium ion composite graphite cathode material |
| CN110581275B (en) * | 2018-06-07 | 2023-03-17 | 山东欧铂新材料有限公司 | Graphene/soft carbon negative electrode material of lithium ion battery, preparation method of graphene/soft carbon negative electrode material and lithium ion battery |
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| CN102779985A (en) * | 2011-05-12 | 2012-11-14 | 北京化工大学 | Graphene modified carbon cathode material and its preparation method |
| CN102306757B (en) * | 2011-08-26 | 2014-07-02 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN103811718B (en) * | 2014-02-20 | 2016-08-17 | 深圳市贝特瑞新能源材料股份有限公司 | The preparation method of a kind of graphene-based composite negative pole material and prepared negative material and lithium ion battery |
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Address after: 116450 Haitang street, Huayuankou Economic Zone, Dalian, Liaoning Patentee after: Dalian Hongguang Lithium Industry Co.,Ltd. Address before: 116450 Haitang street, Huayuankou Economic Zone, Dalian, Liaoning Patentee before: DALIAN HONGGUANG LITHIUM INDUSTRY CO.,LTD. |