CN102786048A - Method for preparing conductive additive for lithium ion batteries - Google Patents
Method for preparing conductive additive for lithium ion batteries Download PDFInfo
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- CN102786048A CN102786048A CN201210298925XA CN201210298925A CN102786048A CN 102786048 A CN102786048 A CN 102786048A CN 201210298925X A CN201210298925X A CN 201210298925XA CN 201210298925 A CN201210298925 A CN 201210298925A CN 102786048 A CN102786048 A CN 102786048A
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- lithium ion
- static eliminator
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002482 conductive additive Substances 0.000 title abstract 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 239000010439 graphite Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 230000003068 static effect Effects 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 3
- 230000002687 intercalation Effects 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008676 import Effects 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 239000006245 Carbon black Super-P Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
A method for preparing conductive additive for lithium ion batteries includes the following steps of firstly, subjecting natural flake graphite to oxidation and layering by concentrated sulfuric acid and potassium permanganate, washing the same to be neutral, drying at the temperature of 50 DEG C to 100 DEG C, expanding for 10-60 seconds at the temperature of 800 DEG C to 1000 DEG C, and obtaining expanded graphite; secondly, adding the expanded graphite into deionized water containing dispersant, adding grinding balls, stirring for 60-300 minutes along with ball milling; and thirdly, spraying and drying slurry after grinding, and obtaining submicron conductive additives with grain size ranging from 0.1 micrometer to 1 micrometer. The conductive additive is smaller than common graphite conductive additive in grain size, and is large in specific surface area and easy to disperse. The method for preparing the conductive additive for lithium ion batteries has the advantages that materials are economical and environment-friendly and easy to obtain; preparation process is simple, production cost is low, and industrialization production is easy to realize, and partial or complete imports can be substituted.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the static eliminator of lithium ion battery, be specifically related to a kind of preparation method of graphite-like carbon material static eliminator.
Background technology
Lithium ion battery have that specific storage is big, sparking voltage is high and steady, low-temperature performance is good, environmental friendliness, safety, the life-span is long, self-discharge is little and ni-mh, the unrivaled advantage of NI-G secondary cell.Since 1991 came out, through the development in surplus ten years, lithium ion battery was dominated the market of small portable battery.
The negative material of lithium ion battery has carbon material, intermetallic compound, tinbase compound etc.Present commercial lithium ion battery adopts carbon material as negative material more.Carbon material negative pole is anodal relatively, and electroconductibility is preferably arranged, and need not add the electroconductibility that static eliminator increases electrode materials in principle.But owing to carbon material is embedding, is deviating from the lithium process, meeting volume expanding and contraction, after the several cycles, the contact between the carbon material can reduce, or the space occurs, causes the electroconductibility of electrode sharply to descend, and therefore needs the suitable static eliminator that adds.Particulate carbon black, acetylene black, or fibrous static eliminator can fill up the space between the carbon material well, keep the stability of electrode in the working cycle, can not cause the electroconductibility of electrode sharply to descend because of the increase of cycle index.
The positive electrode material of lithium ion battery is generally the transition metal oxide compound, as: LiCoO
2, LiNiO
2, LiMnO
2, and LiNi
xCo
yMn
(1-x-y)O
2Deng, and the phosphoric acid salt of transition metal, as: LiMPO
4Their specific conductivity are low, generally are semi-conductor or isolator.Ideal is the mixed conductor of ion and electronics just very, and electron conduction is relevant with anodal electroconductibility quality; Ionic conductivity is relevant with the anodal pore volume, and vesicular structure can provide the storage of electrolytic solution, for the electrode rapid reaction provides the buffer ions source.Static eliminator mainly is to improve anodal electroconductibility in the anodal effect.
Excellent static eliminator need possess following characteristic: one, specific conductivity is higher, and the material of high conductivity can improve the rate of migration of electronics; Two, particle diameter is less, and the material of small particle size can be filled the space of lithium ion battery positive and negative electrode material, makes the contact between the material better, is easy to deviating from, embedding of lithium ion; Three, high-specific surface area, the material that specific surface area is big can contact with the positive and negative electrode material preferably, is easy to the maintenance of electrolytic solution equally, and what be convenient to lithium ion takes off embedding and electronic migration; Four, be easy to disperse, in positive and negative electrode material configuration slurry process, be easy to break up and disperse, can be preferably with the positive and negative electrode material mixing together; Five, high stability can stable existence in the lithium ion battery charging and discharging process, can not volume change take place and influences the cycle performance of battery.
The lithium ion battery static eliminator is mainly Super-P and KS series in the market, and this two series products is all external import, and the former is nano level carbon black series products; Existing smaller particle size and bigger specific surface area have conductivity preferably again, but because particle diameter is less and specific surface area is bigger; Be difficult for disperseing; Be micron-sized electrically conductive graphite then then, be easy to disperse, but conductivity be poor than Super-P.So it is in the actual use, the both adds use simultaneously, complementary not enough.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used for the static eliminator of lithium ion battery; Specifically be used to prepare a kind of superfine; The static eliminator of the graphite-like carbon material of the submicron order (particle diameter be 0.1 μ m～1 μ m) of particle diameter between nano level and micron order; This static eliminator has promptly been avoided because the scattering problem that the static eliminator (Super-P) of nano level particle diameter exists has remedied the relatively poor deficiency of micron-sized electrically conductive graphite (KS) electroconductibility simultaneously.Static eliminator specific surface area of the present invention in the absorbed dose that increases electrolytic solution, also is convenient to the maintenance of electrolytic solution up to 100～300 ㎡ ∕ g simultaneously, has also guaranteed the cyclical stability of lithium ion battery.
Graphite crystal has the hexaplanar laminate structure of being made up of carbon, and the carbon atom on the layer plane is with strong covalent bonds; And layer combines with Van der Waals force with interlayer, and a little less than very, and interlamellar spacing is bigger.Therefore, under suitable condition, number of chemical materials such as acid, basic metal, salt can insert graphite layers, and combine to form new chemofacies-compound between graphite layers with carbon atom.This intercalation compound can decompose rapidly when being heated to proper temperature, produces a large amount of gases, makes graphite expand into vermiform novel substance, i.e. expanded graphite along the C direction of principal axis.Therefore the interlayer of expanded graphite is opened, and bonding force dies down, and more is prone to pulverize and obtains the graphite powder of submicron order.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of preparation method who is used for the static eliminator of lithium ion battery may further comprise the steps:
(1) with the vitriol oil and potassium permanganate with natural flake graphite oxidation intercalation, washing is to neutral, then 50 ℃～100 ℃ oven dry down, 800 ℃～1000 ℃ following expansion process 10～60 seconds, obtains expanded graphite again;
(2) expanded graphite is joined in the deionized water that contains dispersion agent, add mill ball then, stirring ball-milling 60～300 minutes;
(3) slurry after will grinding carries out spraying drying, and obtaining particle diameter is the submicron order static eliminator of 0.1 μ m～1 μ m.
The mass ratio of natural flake graphite, the vitriol oil and potassium permanganate is 1:4～8:0.1～1 among the present invention; The concentration of the said vitriol oil is 90%～98%.
The median size of natural flake graphite among the present invention≤50 μ m, carbon content>=95%.Graphite is in the middle of grinding and processing, and it is more or less freely to be crushed to micron order, but if want to be worked into submicron order, then need more complicated technology and equipment, and production efficiency is very low, so has restricted the application of graphite.
For obtaining the more tiny static eliminator of particle diameter, as preferably, the median size of natural flake graphite≤10 μ m.
As preferably, bake out temperature is 60 ℃～70 ℃ in the step of the present invention (1), if temperature is too high, because graphite granule is thinner, is prone to the caking of reuniting, and influence expansion effect, and too low as if temperature, then drying rate is too slow, influences efficient.
As preferably, the technology of expansion process is expansion process 40 seconds in the retort furnace of 900 ℃ of temperature among the present invention.
Among the present invention set by step (1) expanding volume of handling resulting expanded graphite be 30mL ∕ g～300mL ∕ g.
The inlet temperature of spray-dired warm air is 200 ℃～300 ℃ in the step of the present invention (3), and temperature out is 40 ℃～90 ℃.
Expanded graphite among the present invention: dispersion agent: deionized water: the mass ratio of mill ball is 1:0.1～1:1～5:1～5.
Dispersion agent described in the present invention is one or more in Z 150PH, sodium dodecyl benzenylsulfonate, sodium lauryl sulphate, alcohol and the hydroxymethyl cellulose sodium.
Mill ball described in the present invention is a zirconia ball, and choosing the sphere diameter specification is one or more collocation uses among 2mm～40mm; The rotating speed of used agitating ball mill is 30～300 Zhuan ∕ branches.
Compared with prior art, the present invention has following beneficial effect:
Graphite carbon material conductive agent of the present invention has littler particle diameter than common graphite-like static eliminator, and high specific surface area is easy to disperse simultaneously, and in addition, adopt this method also to have the following advantages: 1, raw material economics environmental protection is easy to get; 2, preparation technology is simple, and production cost is low, is easy to suitability for industrialized production; 3, can partly substitute or substitute fully import.
Description of drawings
Fig. 1 is the SEM figure of the embodiment of the invention 1 prepared static eliminator.
Fig. 2 is the cycle performance figure of the embodiment of the invention 1.
Fig. 3 is the cycle performance figure of Comparative Examples 1 of the present invention.
Embodiment
Be easy to understand and understand in order to make technique means of the present invention, creation characteristic, workflow, method of use reach purpose and effect, below further set forth the present invention.
Embodiment 1
Take by weighing a certain amount of natural flake graphite (D50 is 6 μ m, carbon content >=99%), press graphite: the vitriol oil: the mass ratio of potassium permanganate=1:7:0.2; Add the vitriol oil earlier and be stirred to evenly, and then add potassium permanganate slowly, add continued and stir 60min; Water is washed till neutrality again, and 70 ℃ of oven dry down, expansion process is 40 seconds in the retort furnace of 900 ℃ of temperature then; Obtain expanded graphite, with expanded graphite: alcohol: deionized water: mill ball joins in the agitating ball mill by mass ratio=1:0.4:4:3, and rotating speed is 180 Zhuan ∕ branches; The ball milling time is 120 minutes; Spraying drying is collected dried powder then, is the static eliminator that is used for lithium ion battery of the present invention.
The detected result of physicals is seen table 1:
Table 1
The detection of chemical property:
Static eliminator of the present invention is carried out the produced with combination battery with anode material for lithium-ion batteries and negative material respectively.Positive electrode material, static eliminator, sticker PVDF be according to mass ratio 100:2.5:2, after doing solvent and evenly size mixing with NMP, is applied on the aluminium foil; Under 100 ℃, vacuumize drying, then negative material, static eliminator, CMC, SBR are pressed mass ratio 100:1.5:2:5.5, after doing solvent and evenly size mixing with deionized water; Be applied on the Copper Foil; Under 90 ℃, vacuumize drying, with dried positive and negative electrode pole piece through roll-in, cut-parts, coiling, fluid injection, seal, formation process, process 18650 cylindrical batteries; Employed positive electrode material is a cobalt acid lithium; Negative material is a synthetic graphite, and barrier film is Celgard2400, and electrolytic solution is 1M LiPF6 ∕ DMC:EC:DEC.
On the automatic detecting box of lithium-ion secondary cell, above-mentioned battery is carried out electrochemical property test, content measurement comprises the capacity circulation conservation rate of the internal resistance of cell, 1C impulse electricity.Cyclic curve figure sees Fig. 2, and detected result is seen table 2.
Comparative Examples 1
It is compound to adopt Super-P and KS-6 to carry out as static eliminator and anode material for lithium-ion batteries, and wherein positive electrode material, Super-P, KS-6, sticker PVDF be according to mass ratio 100:1.5:1:2, after doing solvent and evenly size mixing with NMP; Be applied on the aluminium foil, under 100 ℃, vacuumize drying, then negative material, Super-P, CMC, SBR are pressed mass ratio 100:1.5:2:5.5; After doing solvent and evenly size mixing with deionized water, be applied on the Copper Foil, under 90 ℃, vacuumize drying; With dried positive and negative electrode pole piece through roll-in, cut-parts, coiling, fluid injection, seal, formation process; Process 18650 cylindrical batteries, employed positive electrode material is a cobalt acid lithium, and negative material is a synthetic graphite; Barrier film is Celgard2400, and electrolytic solution is 1M LiPF6 ∕ DMC:EC:DEC.
On the automatic detecting box of lithium-ion secondary cell, above-mentioned battery is carried out electrochemical property test, content measurement comprises the capacity circulation conservation rate of the internal resistance of cell, 1C impulse electricity.Cyclic curve figure sees Fig. 3, and detected result is seen table 2.
Table 2
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The protection domain that requires of the present invention is defined by appending claims and equivalent thereof.
Claims (11)
1. preparation method who is used for the static eliminator of lithium ion battery is characterized in that: may further comprise the steps:
(1) with the vitriol oil and potassium permanganate with natural flake graphite oxidation intercalation, washing is to neutral, then 50 ℃～100 ℃ oven dry down, 800 ℃～1000 ℃ following expansion process 10～60 seconds, obtains expanded graphite again;
(2) expanded graphite is joined in the deionized water that contains dispersion agent, add mill ball then, stirring ball-milling 60～300 minutes;
(3) slurry after will grinding carries out spraying drying, and obtaining particle diameter is the submicron order static eliminator of 0.1 μ m～1 μ m.
2. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1 is characterized in that: the mass ratio of natural flake graphite, the vitriol oil and potassium permanganate is 1:4～8:0.1～1; The concentration of the said vitriol oil is 90%～98%.
3. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1 and 2 is characterized in that: the median size of natural flake graphite≤50 μ m, carbon content>=95%.
4. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1 and 2 is characterized in that: the median size of said natural flake graphite≤10 μ m.
5. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1 is characterized in that: bake out temperature is 60 ℃～70 ℃ in the step (1).
6. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1 is characterized in that: the technology of step (1) expansion process is expansion process 40 seconds in the retort furnace of 900 ℃ of temperature.
7. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1 is characterized in that: the expanding volume of the resulting expanded graphite of (1) processing is 30mL ∕ g～300mL ∕ g set by step.
8. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1 is characterized in that: the inlet temperature of spray-dired warm air is 200 ℃～300 ℃ in the step (3), and temperature out is 40 ℃～90 ℃.
9. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1 is characterized in that: expanded graphite: dispersion agent: deionized water: the mass ratio of mill ball is 1:0.1～1:1～5:1～5.
10. according to claim 1 or 9 described a kind of preparing methods that are used for the static eliminator of lithium ion battery, it is characterized in that: described dispersion agent is one or more in Z 150PH, sodium dodecyl benzenylsulfonate, sodium lauryl sulphate, alcohol and the hydroxymethyl cellulose sodium.
11. a kind of preparation method who is used for the static eliminator of lithium ion battery according to claim 1, it is characterized in that: described mill ball is a zirconia ball, and choosing the sphere diameter specification is one or more collocation uses among 2mm～40mm; The rotating speed of used agitating ball mill is 30～300 Zhuan ∕ branches.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367765A (en) * | 2013-07-25 | 2013-10-23 | 哈尔滨工业大学 | Preparation method of multilayer graphite and method for preparing lithium-air battery cathode by using multilayer graphite |
| CN103387229A (en) * | 2013-07-23 | 2013-11-13 | 哈尔滨工业大学 | A preparation method for porous graphene and a preparation method for a graphene-based aluminium-air cell |
| CN103647083A (en) * | 2013-11-15 | 2014-03-19 | 成都兴能新材料有限公司 | Preparation method of composite graphitic carbon cathode material |
| CN104505515A (en) * | 2014-12-26 | 2015-04-08 | 广东东莞市天润电子材料有限公司 | Nano-graphite conductive agent for lithium iron phosphate battery and preparation method of conductive agent |
| CN108963192A (en) * | 2017-05-26 | 2018-12-07 | 丰田自动车株式会社 | The manufacturing method of anode for nonaqueous electrolyte secondary battery and the manufacturing method of non-aqueous electrolyte secondary battery |
Citations (5)
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| CN103367765B (en) * | 2013-07-25 | 2015-09-16 | 哈尔滨工业大学 | This Multi-layer graphite of the preparation method and application of Multi-layer graphite prepares the method for lithium-air battery cathode |
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| CN103647083B (en) * | 2013-11-15 | 2015-12-02 | 成都兴能新材料有限公司 | The preparation method of composite plumbago-carbon negative pole material |
| CN104505515A (en) * | 2014-12-26 | 2015-04-08 | 广东东莞市天润电子材料有限公司 | Nano-graphite conductive agent for lithium iron phosphate battery and preparation method of conductive agent |
| CN108963192A (en) * | 2017-05-26 | 2018-12-07 | 丰田自动车株式会社 | The manufacturing method of anode for nonaqueous electrolyte secondary battery and the manufacturing method of non-aqueous electrolyte secondary battery |
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