CN103086363A - 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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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 utilize graphite microparticles to prepare the method for ion cathode material lithium.
Background technology
As the negative material of lithium ion battery, the current potential to lithium when requiring negative material embedding lithium and removal lithium embedded is more low better, can obtain high cell voltage like this.Material should have higher weight, volume and capacity ratio and good cycle performance, and to electrolytical favorable compatibility.For a long time, both at home and abroad many materials are studied and explore, but up to now, only have carbon materials can successfully be used as lithium ion battery negative material.Take the lead in successfully using refinery coke as ion cathode material lithium from the beginning of the nineties in last century from Sony corporation of Japan, since realizing the lithium ion battery commercialization, the Application and Development of new carbon has obtained great promotion.Carbon materials is of a great variety, as synthetic graphite (addition product and residue in through-stone oil coke refining process, for example: pitch, pitch coke, refinery coke ...), natural graphite, coal (coal-tar pitch) coke, amorphous graphite, bamboo carbon, wooden carbon, and other Polymer-pyrolysis carbon ... all belong to the carbon materials category.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of 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 that obtains has that high-quality and safety is reliable, the pole piece compacted density is high, the advantage that has extended cycle life.
The present invention solves the problems of the technologies described above the technical scheme that adopts: utilizes graphite microparticles to prepare the method for ion cathode material lithium, in turn includes the following steps,
1) select materials A, material B, material C and material D,
Described materials A is obtained with stage treatment through milling by synthetic graphite, and granularity D50 is 12-26 μ m;
Described material B is obtained with spheroidizing through milling by natural graphite, and granularity D50 is 7-22 μ m;
Described material C is obtained through milling by synthetic graphite, and granularity D50 is 12-26 μ m;
Described material D is that synthetic graphite or the natural graphite granularity that produces of milling is the micro mist of 3-7 μ m;
At least a and described materials A in material B and material C, described material D are mixed, obtain mixing material E;
2) gained mixing material E is added pitch soak roasting and coat, barometric point 8-10kPa soaks 7 ~ 9 hours roasting time, obtains the numb spherical particle after polymerization;
3) with described step 2) the numb spherical particle that obtains is at temperature 500-1500 ℃, and the time is 10-20 days solidifying formations; Carry out high temperature graphitization at 2600 ~ 3200 ℃ again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
Further technical scheme, described step 2) in, the add-on of described pitch is 20%-40% according to the Mass Calculation with respect to mixing material E.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 of described materials A, material B, material C≤60-120 μ m.
In described step 1), the mass ratio when described materials A, material B, material C and four kinds of materials of material D mix is 10-50:10-60:10-50:10-60.
In described step 3), described high temperature graphitization temperature is 3000 ~ 3200 ℃.
Described step 1) in, " materials A is milled by synthetic graphite and stage treatment obtains, and granularity D50 is 12-26 μ m; ", " material C is milled by synthetic graphite and is obtained, and granularity D50 is 12-26 μ m; " wherein milling is prior art with stage treatment.
The preparation of material C can be: can directly obtain after milling through grinding equipment.
The preparation of materials A can be: add grading machine (for example air classifier) in grinding equipment, obtain by air classification.
Compared with prior art, the advantage that has of the present invention is:
(1) in synthetic graphite and natural graphite are milled the whole process of preparation negative material, can produce a large amount of graphite microparticles, this graphite microparticles granularity is 3-7 μ m, i.e. material D in the present invention.Generally, this synthetic graphite or the natural graphite micro mist (granularity is 3-7 μ m) of milling and producing; Because particle diameter is meticulous, and product structure is loose, can only be as controlling the fields such as gold, machinery, electronics, usually processed at a low price as rejected material by negative material manufacturer.The present invention utilizes this discarded graphite microparticles (being material D), and the 2-3 kind in itself and other 3 kinds of graphite cathode raw materials (materials A, material B and material C) is mixed in proportion, then by polymerization, it is integrated, adding 20-40% pitch to soak roasting coats, by the negative material of this kind technique, can be directly as the negative electrode for lithium ion battery material or as the lithium ion battery negative material subsidiary material.Therefore, the present invention has improved the utilization ratio of graphite raw material, has the effect of utilization of waste material.
(2) method of through performance complementation of the present invention to make up the loose characteristic of graphite microparticles structure (being material D), is brought into play the security of synthetic graphite, long circulation with heavy body, the processibility of natural graphite effectively.The ion cathode material lithium that finally prepares has that high-quality and safety is reliable, the pole piece compacted density is high, the advantage that has extended cycle life.Gained negative material gram specific storage 330mAh/g, first charge-discharge efficiency 92%, processing characteristics is excellent, and the pole piece compacted density reaches 〉=1.7g/cm
3, be applicable to: all kinds of liquid lithium ions and polymer Li-ion battery and flexible packing lithium ion, power lithium-ion battery production also can be used as the lithium ion battery negative material subsidiary material to improve the over-all properties of negative material.
(3) preparation method's simple process of the present invention fast, pollute little, can greatly enhance productivity, greatly increased the added value of graphite microparticles, turn waste into wealth, be fit to batch production.
Embodiment
The below will describe in detail according to a preferred embodiment of the invention.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 synthetic graphite and stage treatment obtains, and granularity D50 is 12-26 μ m;
Material B is milled by natural graphite and spheroidizing obtains, and granularity D50 is 7-22 μ m;
Material D is that synthetic graphite or the natural graphite granularity that produces of milling is the micro mist of 3-7 μ m;
And control the Dmax of described materials A, material B≤60-120 μ m.
With above-mentioned four kinds of materials, materials A, material B, material D mix according to mass ratio 10-50:10-60:10-60, get mixing material E.
2) gained mixing material E being added 20%-40%(take the quality of mixing material E as benchmark) pitch soaks roasting and coats, and barometric point 8-10kPa soaks 7 ~ 9 hours roasting time, obtains the numb spherical particle after polymerization;
3) with described step 2) the numb spherical particle that obtains is at temperature 500-1500 ℃, and the time is 10-20 days solidifying formations; Carry out high temperature graphitization at 2800 ~ 3000 ℃ again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
4) the ion cathode material lithium machinery with gained after described step 3) high temperature graphitization is modified into ellipticity, obtains the high ion cathode material lithium of cost performance.
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 storage 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 synthetic graphite and stage treatment obtains, and granularity D50 is 12-26 μ m;
Material C is milled by synthetic graphite and is obtained, and granularity D50 is 12-26 μ m;
Material D is that synthetic graphite or the natural graphite granularity that produces of milling is the micro mist of 3-7 μ m; And control the Dmax of described materials A, material C≤60-120 μ m.With above-mentioned four kinds of materials, materials A, material B, material D mix according to mass ratio 10-50:10-60:10-60, get mixing material E.
2) gained mixing material E being added 20%-40%(take the quality of mixing material E as benchmark) pitch soaks roasting and coats, and barometric point 8-10kPa soaks 7 ~ 9 hours roasting time, obtains the numb spherical particle after polymerization;
3) with described step 2) the numb spherical particle that obtains is at temperature 500-1500 ℃, and the time is 10-20 days solidifying formations; Carry out high temperature graphitization at 3000 ~ 3200 ℃ again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
4) the ion cathode material lithium machinery with gained after described step 3) high temperature graphitization is modified into ellipticity, obtains the high ion cathode material lithium of cost performance.
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 storage 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 synthetic graphite and stage treatment obtains, and granularity D50 is 12-26 μ m;
Material B is milled by natural graphite and spheroidizing obtains, and granularity D50 is 7-22 μ m;
Material C is milled by synthetic graphite and is obtained, and granularity D50 is 12-26 μ m;
Material D is that synthetic graphite or the natural graphite granularity that produces of milling is the micro mist of 3-7 μ m; And control the Dmax of described materials A, material B and material C≤60-120 μ m.With 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, get mixing material E.
2) gained mixing material E being added 20%-40%(take the quality of mixing material E as benchmark) pitch soaks roasting and coats, and barometric point 8-10kPa soaks 7 ~ 9 hours roasting time, obtains the numb spherical particle after polymerization;
3) with described step 2) the numb spherical particle that obtains is at temperature 500-1500 ℃, and the time is 10-20 days solidifying formations; Carry out high temperature graphitization at 3000 ~ 3200 ℃ again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
4) the ion cathode material lithium machinery with gained after described step 3) high temperature graphitization is modified into ellipticity, obtains the high ion cathode material lithium of cost performance.
In step 1) in the present embodiment, the mass ratio that materials A, material B, material C, material D mix particularly, can be for example 10 mass parts materials A, 10 mass parts material B, and 10 mass parts material C, 10 mass parts material D mix; Can be also 10 mass parts materials A, 20 mass parts material B, 20 mass parts material C, 20 mass parts material D mix; Can be also 10 mass parts materials A, 30 mass parts material B, 30 mass parts material C, 30 mass parts material D mix; Can be also 10 mass parts materials A, 40 mass parts material B, 40 mass parts material C, 40 mass parts material mixing; Can be also 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 storage is 330mAh/g, compacted density 〉=1.70g/cm
3
Claims (5)
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) select materials A, material B, material C and material D,
Described materials A is obtained with stage treatment through milling by synthetic graphite, and granularity D50 is 12-26 μ m;
Described material B is obtained with spheroidizing through milling by natural graphite, and granularity D50 is 7-22 μ m;
Described material C is obtained through milling by synthetic graphite, and granularity D50 is 12-26 μ m;
Described material D is that synthetic graphite or the natural graphite granularity that produces of milling is the micro mist of 3-7 μ m;
At least a and described materials A in material B and material C, described material D are mixed, obtain mixing material E;
2) gained mixing material E is added pitch soak roasting and coat, barometric point 8-10kPa soaks 7 ~ 9 hours roasting time, obtains the numb spherical particle after polymerization;
3) with described step 2) the numb spherical particle that obtains is at temperature 500-1500 ℃, and the time is 10-20 days solidifying formations; Carry out high temperature graphitization at 2600 ~ 3200 ℃ again, the time is 7 ~ 15 days, obtains ion cathode material lithium.
2. the method for utilizing graphite microparticles to prepare ion cathode material lithium according to claim 1, is characterized in that, 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.
3. the method for utilizing graphite microparticles to prepare ion cathode material lithium according to claim 1, is characterized in that, in described step 1), and the Dmax of described materials A, material B, material C≤60-120 μ m.
4. the described method of utilizing graphite microparticles to prepare ion cathode material lithium of according to claim 1-4 any one, it is characterized in that, in described step 1), the mass ratio when described materials A, material B, material C and four kinds of materials of material D mix is 10-50:10-60:10-50:10-60.
5. the method for utilizing graphite microparticles to prepare ion cathode material lithium according to claim 5, is characterized in that, in described step 3), described high temperature graphitization temperature is 3000 ~ 3200 ℃.
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Cited By (5)
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| CN104425823A (en) * | 2013-09-11 | 2015-03-18 | 宁波杉杉新材料科技有限公司 | Artificial graphite cathode material of lithium ion battery and preparation method of artificial graphite cathode material |
| CN104779396A (en) * | 2015-04-22 | 2015-07-15 | 大连宏光锂业股份有限公司 | Production method of lithium ion composite graphite cathode material |
| CN105826517A (en) * | 2016-06-13 | 2016-08-03 | 周虎 | Carbon film lithium ion battery anode and production method |
| CN107134591A (en) * | 2016-02-26 | 2017-09-05 | 丰田自动车株式会社 | The manufacture method of active material, solid state battery and active material |
| 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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| 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 |
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| CN104425823A (en) * | 2013-09-11 | 2015-03-18 | 宁波杉杉新材料科技有限公司 | Artificial graphite cathode material of lithium ion battery and preparation method of artificial graphite cathode material |
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| CN107134591A (en) * | 2016-02-26 | 2017-09-05 | 丰田自动车株式会社 | The manufacture method of active material, solid state battery and active material |
| CN107134591B (en) * | 2016-02-26 | 2019-03-08 | 丰田自动车株式会社 | The manufacturing method of active material, solid state battery and 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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