CN103086363B - Method for preparing lithium-ion negative material by utilizing graphite micro-powder - Google Patents
Method for preparing lithium-ion negative material by utilizing graphite micro-powder Download PDFInfo
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- CN103086363B CN103086363B CN201210564334.2A CN201210564334A CN103086363B CN 103086363 B CN103086363 B CN 103086363B CN 201210564334 A CN201210564334 A CN 201210564334A CN 103086363 B CN103086363 B CN 103086363B
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Abstract
The invention discloses a method for preparing a lithium-ion negative material by utilizing graphite micro-powder. The method comprises the following steps in sequence: 1) selecting a material A, a material B, a material C and a material D, wherein the material A is prepared by steps of grinding and treating artificial graphite grade by grade, the material B is prepared by steps of grinding and nodulizing natural graphite, the material C is prepared by step of grinding the artificial graphite, and the material D is the micro-powder produced by grinding the artificial graphite or the natural graphite; and mixing at least one of the material B and the material C with the material A and the material D, so as to obtain a mixed material E; 2) adding asphalt, soaking, curing and coating to obtain polymerized pitted ball shaped particles; and 3) curing at 500 to 1500 DEG C, and graphitizing at a high temperature of 2600 to 3200 DEG C, so as to obtain the lithium-ion negative material. According to the method, the negative material of a lithium-ion cell is prepared from the out-of-service graphite micro-powder, and the prepared negative material is high-quality, safe, reliable and has long recycle life; and the compaction density of pole pieces is high.
Description
Technical field
The invention belongs to the preparing technical field of lithium ion battery negative material, particularly, the present invention relates to the method utilizing graphite microparticles to prepare ion cathode material lithium.
Background technology
As the negative material of lithium ion battery, more low better to the current potential of lithium when requiring the embedding lithium of negative material and removal lithium embedded, high cell voltage can be obtained like this.Material should have higher weight, volume and capacity ratio and excellent cycle performance, and to electrolytical favorable compatibility.For a long time, both at home and abroad many materials are studied and are explored, but up to now, only have carbon materials successfully can be used as lithium ion battery negative material.Take the lead in successfully using petroleum coke as ion cathode material lithium from the beginning of the nineties in last century from Sony corporation of Japan, since realizing lithium ion battery commercialization, the Application and Development of new carbon obtains great promotion.Carbon materials is of a great variety, as Delanium (addition product in through-stone oil coke refining process and residue, such as: pitch, pitch coke, petroleum coke ...), native graphite, coal (coal tar pitch) coke, amorphous graphite, bamboo carbon, wooden carbon and other Polymer-pyrolysis carbon ... all belong to carbon materials category.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method utilizing graphite microparticles to prepare ion cathode material lithium, the method prepares lithium ion battery negative material with discarded graphite microparticles, the negative material material obtained has that high-quality and safety is reliable, pole piece compaction density is high, the advantage had extended cycle life.
The present invention solves the problems of the technologies described above adopted technical scheme: utilize graphite microparticles to prepare the method for ion cathode material lithium, in turn include the following steps,
1) the selection of material A, material B, material C and material D,
Described materials A is milled by Delanium process and classification process obtains, and granularity D50 is 12-26 μm;
Described material B is milled by native graphite process and spheroidising obtains, and granularity D50 is 7-22 μm;
Described material C is obtained through milling by Delanium, and granularity D50 is 12-26 μm;
Described material D for Delanium or native graphite produced granularity of milling be the micro mist of 3-7 μm;
At least one in material B and material C is mixed with described materials A, described material D, obtains composite material E;
2) gained composite material E is added pitch leaching roasting coated, atmospheric pressure 8-10kPa, 7 ~ 9 hours roasting time of leaching, obtain the numb spherical particle after being polymerized;
3) by described step 2) the numb spherical particle that obtains is at temperature 500-1500 DEG C, and the time is 10-20 days solidified formings; Carry out high temperature graphitization at 2600 ~ 3200 DEG C again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
Further technical scheme, described step 2) in, the addition of described pitch, according to the Mass Calculation relative to composite material E, is 20%-40%.And preferred mid temperature pitch.
The present invention utilizes graphite microparticles to prepare the method for ion cathode material lithium, also comprises step 4), and described step 4) is: the ion cathode material lithium of gained after described step 3) high temperature graphitization is modified into ellipticity.
In described step 1), the Dmax≤60-120 μm of described materials A, material B, material C.
In described step 1), mass ratio when described materials A, material B, material C and material D tetra-kinds of materials mix is 10-50:10-60:10-50:10-60.
In described step 3), described high temperature graphitization temperature is 3000 ~ 3200 DEG C.
Described step 1) in, " materials A is milled by Delanium and classification process obtains, and granularity D50 is 12-26 μm; ", " material C is milled by Delanium and is obtained, and granularity D50 is 12-26 μm; " wherein mill and classification process be prior art.
The preparation of material C can be: can directly obtain after grinding equipment is milled.
The preparation of materials A can be: in grinding equipment, add grader (such as gas flow sizing machine), obtained by air current classifying.
Compared with prior art, the advantage that the present invention has is:
(1) mill at Delanium and native graphite and prepare in the whole process of negative material, can produce a large amount of graphite microparticles, this graphite microparticles granularity is 3-7 μm, the material D namely in the present invention.Generally, micro mist (granularity is 3-7 μm) milled produced by this Delanium or native graphite; Because particle diameter is meticulous, and product structure is loose, as controlling the fields such as gold, machinery, electronics, usually can only be processed at a low price as obsolete material by negative material manufacturer.The present invention utilizes this discarded graphite microparticles (i.e. material D), and it is mixed in proportion with the 2-3 kind in other 3 kinds of graphite cathode raw materials (materials A, material B and material C), then integrated by polymerization, add 20-40% pitch carry out leaching roasting coated, by the negative material of this kind of technique, can directly as cathode material of lithium ion battery or as lithium ion battery negative material auxiliary material.Therefore, invention increases the utilance of graphite raw material, there is the effect of twice laid.
(2) the present invention is by the method for performance complement, to make up the loose characteristic of graphite microparticles structure (i.e. material D), the high power capacity of the fail safe of Delanium, long circulating and native graphite, processability is effectively played.The ion cathode material lithium finally prepared has that high-quality and safety is reliable, pole piece compaction density is high, the advantage had extended cycle life.Gained negative material gram specific capacity 330mAh/g, first charge-discharge efficiency 92%, processing characteristics is excellent, and pole piece compaction density reaches>=1.7g/cm
3, be applicable to: all kinds of liquid lithium ion and polymer Li-ion battery and flexible packing lithium ion, power lithium-ion battery are produced, also can as lithium ion battery negative material auxiliary material to improve the combination property of negative material.
(3) preparation method's simple process of the present invention fast, pollute little, can greatly enhance productivity, considerably increase the added value of graphite microparticles, turn waste into wealth, be applicable to batch production.
Embodiment
To describe in detail according to a preferred embodiment of the invention below.The following examples can make the present invention of those skilled in the art's comprehend, but do not limit the present invention in any way.
Embodiment 1
Utilize graphite microparticles to prepare the method for ion cathode material lithium, in turn include the following steps:
1) select following three kinds of materials, comprising:
Materials A is milled by Delanium and classification process obtains, and granularity D50 is 12-26 μm;
Material B is milled by native graphite and spheroidising obtains, and granularity D50 is 7-22 μm;
Material D for Delanium or native graphite produced granularity of milling be the micro mist of 3-7 μm;
And control the Dmax≤60-120 μm of described materials A, material B.
By above-mentioned four kinds of materials, materials A, material B, material D mix according to mass ratio 10-50:10-60:10-60, obtain composite material E.
2) gained composite material E is added 20%-40%(with the quality of composite material E for benchmark) pitch leaching roasting coated, atmospheric pressure 8-10kPa, leaching 7 ~ 9 hours roasting time, obtain be polymerized after numb spherical particle;
3) by described step 2) the numb spherical particle that obtains is at temperature 500-1500 DEG C, and the time is 10-20 days solidified formings; Carry out high temperature graphitization at 2800 ~ 3000 DEG C again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
4) the ion cathode material lithium machinery of gained after described step 3) high temperature graphitization is modified into ellipticity, obtains the ion cathode material lithium that cost performance is high.
The ion cathode material lithium first charge-discharge efficiency 91.5% that the cost performance that embodiment 1 prepares is high, negative material gram specific capacity is 325mAh/g, compacted density>=1.6g/cm
3.
Embodiment 2
Utilize graphite microparticles to prepare the method for ion cathode material lithium, in turn include the following steps:
1) select following three kinds of materials, comprising:
Materials A is milled by Delanium and classification process obtains, and granularity D50 is 12-26 μm;
Material C is milled by Delanium and is obtained, and granularity D50 is 12-26 μm;
Material D for Delanium or native graphite produced granularity of milling be the micro mist of 3-7 μm; And control the Dmax≤60-120 μm of described materials A, material C.By above-mentioned four kinds of materials, materials A, material B, material D mix according to mass ratio 10-50:10-60:10-60, obtain composite material E.
2) gained composite material E is added 20%-40%(with the quality of composite material E for benchmark) pitch leaching roasting coated, atmospheric pressure 8-10kPa, leaching 7 ~ 9 hours roasting time, obtain be polymerized after numb spherical particle;
3) by described step 2) the numb spherical particle that obtains is at temperature 500-1500 DEG C, and the time is 10-20 days solidified formings; Carry out high temperature graphitization at 3000 ~ 3200 DEG C again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
4) the ion cathode material lithium machinery of gained after described step 3) high temperature graphitization is modified into ellipticity, obtains the ion cathode material lithium that cost performance is high.
The ion cathode material lithium first charge-discharge efficiency 91.5% that the cost performance that embodiment 2 prepares is high, negative material gram specific capacity is 325mAh/g, compacted density>=1.65g/cm
3.
Embodiment 3
Utilize graphite microparticles to prepare the method for ion cathode material lithium, in turn include the following steps:
1) select following four kinds of materials, comprising:
Materials A is milled by Delanium and classification process obtains, and granularity D50 is 12-26 μm;
Material B is milled by native graphite and spheroidising obtains, and granularity D50 is 7-22 μm;
Material C is milled by Delanium and is obtained, and granularity D50 is 12-26 μm;
Material D for Delanium or native graphite produced granularity of milling be the micro mist of 3-7 μm; And control the Dmax≤60-120 μm of described materials A, material B and material C.By above-mentioned four kinds of materials, materials A, material B, material C, material D mix according to mass ratio 10-50:10-60:10-50:10-60, obtain composite material E.
2) gained composite material E is added 20%-40%(with the quality of composite material E for benchmark) pitch leaching roasting coated, atmospheric pressure 8-10kPa, leaching 7 ~ 9 hours roasting time, obtain be polymerized after numb spherical particle;
3) by described step 2) the numb spherical particle that obtains is at temperature 500-1500 DEG C, and the time is 10-20 days solidified formings; Carry out high temperature graphitization at 3000 ~ 3200 DEG C again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
4) the ion cathode material lithium machinery of gained after described step 3) high temperature graphitization is modified into ellipticity, obtains the ion cathode material lithium that cost performance is high.
In step 1) in the present embodiment, the mass ratio of materials A, material B, material C, material D mixing particularly, such as, can be 10 mass parts materials A, 10 mass parts material B, 10 mass parts material C, and 10 mass parts material D mix; Also can be 10 mass parts materials A, 20 mass parts material B, 20 mass parts material C, 20 mass parts material D mix; Also can be 10 mass parts materials A, 30 mass parts material B, 30 mass parts material C, 30 mass parts material D mix; Also can be 10 mass parts materials A, 40 mass parts material B, 40 mass parts material C, 40 mass parts material mixing; Also can be 10 mass parts materials A, 60 mass parts material B, 50 mass parts material C, 60 mass parts material mixing.
The ion cathode material lithium first charge-discharge efficiency 92% that the cost performance that embodiment 3 prepares is high, negative material gram specific capacity is 330mAh/g, compacted density>=1.70g/cm
3.
Claims (4)
1. utilize graphite microparticles to prepare the method for ion cathode material lithium, it is characterized in that, in turn include the following steps,
1) the selection of material A, material B, material C and material D,
Described materials A is milled by Delanium process and classification process obtains, and granularity D50 is 12-26 μm;
Described material B is milled by native graphite process and spheroidising obtains, and granularity D50 is 7-22 μm;
Described material C is obtained through milling by Delanium, and granularity D50 is 12-26 μm;
Described material D for Delanium or native graphite produced granularity of milling be the micro mist of 3-7 μm;
At least one in material B and material C is mixed with described materials A, described material D, obtains composite material E;
2) gained composite material E is added pitch leaching roasting coated, atmospheric pressure 8-10kPa, 7 ~ 9 hours roasting time of leaching, obtain the numb spherical particle after being polymerized;
3) by described step 2) the numb spherical particle that obtains is at temperature 500-1500 DEG C, and the time is 10-20 days solidified formings; Carry out high temperature graphitization at 2600 ~ 3200 DEG C again, the time is 7 ~ 15 days, obtains ion cathode material lithium;
Described step 1) in, mass ratio when described materials A, material B, material C and material D tetra-kinds of materials mix is 10-50:10-60:10-50:10-60;
Described step 2) in, the addition of described pitch, according to the Mass Calculation relative to composite material E, is 20%-40%.
2. the method utilizing graphite microparticles to prepare ion cathode material lithium according to claim 1, it is characterized in that, also comprise step 4), described step 4) be: by described step 3) ion cathode material lithium of gained is modified into ellipticity after high temperature graphitization.
3. the method utilizing graphite microparticles to prepare ion cathode material lithium according to claim 1, is characterized in that, described step 1) in, the Dmax≤60-120 μm of described materials A, material B, material C.
4. the graphite microparticles that utilizes according to claim 1-3 any one prepares the method for ion cathode material lithium, it is characterized in that, described step 3) in, described high temperature graphitization temperature is 3000 ~ 3200 DEG C.
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| CN104425823B (en) * | 2013-09-11 | 2019-04-19 | 宁波杉杉新材料科技有限公司 | A kind of artificial graphite cathode material for lithium ion batteries and preparation method thereof |
| 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 |
| JP6323475B2 (en) * | 2016-02-26 | 2018-05-16 | トヨタ自動車株式会社 | Composite active material, solid battery, and method for producing composite active material |
| CN105826517A (en) * | 2016-06-13 | 2016-08-03 | 周虎 | Carbon film lithium ion battery anode and production method |
| CN108217639A (en) * | 2018-01-15 | 2018-06-29 | 天津锦美碳材科技发展有限公司 | Compound lithium ion battery negative material and preparation method thereof |
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