CN102786048B - Method for preparing conductive additive for lithium ion batteries - Google Patents
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- CN102786048B CN102786048B CN201210298925.XA CN201210298925A CN102786048B CN 102786048 B CN102786048 B CN 102786048B CN 201210298925 A CN201210298925 A CN 201210298925A CN 102786048 B CN102786048 B CN 102786048B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- 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 36
- 239000010439 graphite Substances 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000006258 conductive agent Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 12
- 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
- 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
- 230000002687 intercalation Effects 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 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
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 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
- 238000001035 drying Methods 0.000 abstract description 3
- 230000008676 import Effects 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 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
- 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
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 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
- 239000011230 binding agent Substances 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
- 239000002131 composite material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 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
- 238000005755 formation reaction Methods 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
- 239000000843 powder Substances 0.000 description 2
- 238000007789 sealing Methods 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
- 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 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 230000000295 complement effect Effects 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
- 238000009831 deintercalation Methods 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
- 239000008187 granular material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 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
- 239000002105 nanoparticle Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium 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
Classifications
-
- 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
- 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 of the conductive agent for lithium ion battery, be specifically related to a kind of preparation method of graphite-like carbon material conductive agent.
Background technology
Lithium ion battery has that specific storage is large, 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 come out, through the development of more than 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, tin-based composites etc.Current commercial lithium ion battery adopts carbon material as negative material more.Carbon material negative pole is relatively anodal, has good electroconductibility, need not add in principle conductive agent to increase the electroconductibility of electrode materials.But because carbon material is embedding, deviating from lithium process, volumetric expansion and contraction can occur, after several circulations, the contact between carbon material can reduce, or occurs space, causes the electroconductibility of electrode sharply to decline, and therefore needs suitably to add conductive agent.Carbon black, acetylene black or the fibrous conductive agent of particle can be filled up the space between carbon material well, keep the stability of electrode in working cycle, can sharply not decline because the increase of cycle index causes the electroconductibility of electrode.
The positive electrode material of lithium ion battery is generally 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
4; Their specific conductivity are low, are generally semi-conductor or isolator.Desirable just very ion and the mixed conductor of electronics, electron conduction is relevant with anodal electroconductibility quality; Ionic conductivity is relevant with anodal pore volume, and vesicular structure can provide the storage of electrolytic solution, for electrode rapid reaction provides buffer ions source.Conductive agent is mainly to improve anodal electroconductibility in anodal effect.
Excellent conductive agent need to possess following feature: 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 material better, is easy to deviating from, embedding of lithium ion; Three, high-specific surface area, the material that specific surface area is large can contact with positive and negative electrode material preferably, is easy to equally the maintenance of electrolytic solution, is convenient to deintercalation and the electronic migration of lithium ion; Four, be easy to disperse, in positive and negative electrode material configuration slurry process, be easy to break up and disperse, can be preferably together with positive and negative electrode material mixing; Five, high stability, can stable existence in the process discharging and recharging at lithium ion battery, can not volume change occur and affects the cycle performance of battery.
Lithium ion battery conductive agent is mainly Super-P and KS series in the market, this two series products is all external import, the former is nano level carbon black series products, existing less particle diameter and larger specific surface area, have again good conductivity, but because particle diameter is less and specific surface area is larger, be difficult for disperseing, be then micron-sized electrically conductive graphite, be easy to disperse, but conductivity be poor compared with Super-P.So in actual use procedure, both add and use simultaneously, complementary not enough.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the conductive agent for lithium ion battery; A kind of ultra-fine specifically for preparing, (particle diameter is the conductive agent of 0.1 μ m～1 μ graphite-like carbon material m) to the submicron order of particle diameter between nano level and micron order, the scattering problem that this conductive agent has avoided the conductive agent (Super-P) due to Nano Particle to exist has made up the poor deficiency of micron-sized electrically conductive graphite (KS) electroconductibility simultaneously.Conductive agent specific surface area of the present invention, up to 100～300 ㎡ ∕ g, in increasing the absorbed dose of electrolytic solution, is also convenient to the maintenance of electrolytic solution simultaneously, has also ensured the cyclical stability of lithium ion battery.
Graphite crystal has the hexaplanar laminate structure being made up of carbon, and the carbon atom on layer plane is with strong covalent bonds; And layer is combined with Van der Waals force with interlayer, a little less than very, and interlamellar spacing is larger.Therefore, under suitable condition, the number of chemical materials such as acid, basic metal, salt can insert graphite layers, and are combined with carbon atom and form new chemofacies-compound between graphite layers.This intercalation compound, in the time being heated to proper temperature, can decompose rapidly, produces a large amount of gas, makes graphite expand into vermiform novel substance, i.e. expanded graphite along C direction of principal axis.The interlayer of expanded graphite is opened, and bonding force dies down, and therefore more easily pulverizes and obtains the graphite composite powder of submicron order.
For achieving the above object, the present invention adopts following technical scheme:
For a preparation method for the conductive agent of lithium ion battery, comprise the following steps:
(1) with the vitriol oil and potassium permanganate, natural flake graphite is oxidized to intercalation, is washed to neutrality, then at 50 DEG C～100 DEG C, dry, then at 800 DEG C～1000 DEG C expansion process 10～60 seconds, obtain expanded graphite;
(2) expanded graphite is joined in the deionized water containing dispersion agent, then add mill ball, stirring ball-milling 60～300 minutes;
(3) slurry after grinding is sprayed and is dried, obtaining particle diameter is the submicron order conductive agent of 0.1 μ m～1 μ m.
In the present invention, the mass ratio of natural flake graphite, the vitriol oil and potassium permanganate is 1:4～8:0.1～1; The concentration of the described vitriol oil is 90%～98%.
Median size≤50 μ the m of natural flake graphite in the present invention, carbon content >=95%.Graphite, in the middle of grinding and processing, is crushed to micron order comparatively easy, if but want to be worked into submicron order, need more complicated technology and equipment, and production efficiency is very low, has therefore restricted the application of graphite.
For obtaining the conductive agent that particle diameter is more tiny, as preferably, the median size≤10 μ m of natural flake graphite.
As preferably, in step of the present invention (1), bake out temperature is 60 DEG C～70 DEG C, if temperature is too high, because graphite granule is thinner, the caking of easily reuniting, affects expansion effect, if temperature is too low, drying rate is too slow, affects efficiency.
As preferably, in the present invention, the technique of expansion process is expansion process 40 seconds in the retort furnace of 900 DEG C of temperature.
The expanding volume of processing by step (1) expanded graphite obtaining in the present invention is 30mL ∕ g～300mL ∕ g.
In step of the present invention (3), the inlet temperature of spray-dired warm air is 200 DEG C～300 DEG C, and temperature out is 40 DEG C～90 DEG C.
Expanded graphite in 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 polyvinyl alcohol, sodium dodecyl benzenylsulfonate, sodium lauryl sulphate, alcohol and hydroxymethyl cellulose sodium.
Mill ball described in the present invention is zirconia ball, and choosing sphere diameter specification is one or more the collocation uses in 2mm～40mm; The rotating speed of agitating ball mill used is that 30～300 Zhuan ∕ divide.
Compared with prior art, the present invention has following beneficial effect:
Graphite carbon material conductive agent of the present invention, has less particle diameter than common graphite-like conductive agent, and high specific surface area is easy to disperse simultaneously, in addition, adopts in this way and also has 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 complete replace imported.
Brief description of the drawings
Fig. 1 is the SEM figure of the embodiment of the present invention 1 prepared conductive agent.
Fig. 2 is the cycle performance figure of the embodiment of the present invention 1.
Fig. 3 is the cycle performance figure of comparative example 1 of the present invention.
Embodiment
In order to make technique means of the present invention, creation characteristic, workflow, using method reach object and effect is easy to understand, below further set forth the present invention.
Embodiment 1
(D50 is 6 μ m to take a certain amount of natural flake graphite, carbon content >=99%), press graphite: the vitriol oil: the mass ratio of potassium permanganate=1:7:0.2, first add the vitriol oil to be stirred to evenly, and then add slowly potassium permanganate, add rear continuation and stir 60min, wash with water again to neutrality, then at 70 DEG C, dry, expansion process 40 seconds in the retort furnace of 900 DEG C of temperature, obtain expanded graphite, by expanded graphite: alcohol: deionized water: mill ball in mass ratio=1:0.4:4:3 joins in agitating ball mill, rotating speed is that 180 Zhuan ∕ divide, Ball-milling Time is 120 minutes, then spraying is dry, collect dried powder, be the conductive agent for lithium ion battery of the present invention.
The detected result of physicals is in table 1:
Table 1
The detection of chemical property:
Conductive agent of the present invention is carried out to produced with combination battery with anode material for lithium-ion batteries and negative material respectively.Positive electrode material, conductive agent, binding agent PVDF is according to mass ratio 100:2.5:2, after doing solvent and evenly size mixing with NMP, be applied on aluminium foil, at 100 DEG C, vacuumize dry, then by negative material, conductive agent, CMC, SBR is 100:1.5:2:5.5 in mass ratio, after doing solvent and evenly size mixing with deionized water, be applied on Copper Foil, at 90 DEG C, vacuumize dry, by just dried, cathode pole piece is through roll-in, cut-parts, reel, fluid injection, sealing, formation process, make 18650 cylindrical batteries, the positive electrode material using is cobalt acid lithium, negative material is synthetic graphite, barrier film is Celgard2400, electrolytic solution is 1M LiPF6 ∕ DMC:EC:DEC.
On the automatic detecting box of lithium-ion secondary cell, above-mentioned battery is carried out to electrochemical property test, content measurement comprises the capacity circulating conservation rate of the internal resistance of cell, 1C impulse electricity.Cyclic curve figure is shown in Fig. 2, and detected result is in table 2.
Comparative example 1
Adopt Super-P and KS-6 to carry out compound as conductive agent and anode material for lithium-ion batteries, wherein positive electrode material, Super-P, KS-6, binding agent PVDF is according to mass ratio 100:1.5:1:2, after doing solvent and evenly size mixing with NMP, be applied on aluminium foil, at 100 DEG C, vacuumize dry, then by negative material, Super-P, CMC, SBR is 100:1.5:2:5.5 in mass ratio, after doing solvent and evenly size mixing with deionized water, be applied on Copper Foil, at 90 DEG C, vacuumize dry, by just dried, cathode pole piece is through roll-in, cut-parts, reel, fluid injection, sealing, formation process, make 18650 cylindrical batteries, the positive electrode material using is cobalt acid lithium, negative material is synthetic graphite, barrier film is Celgard2400, electrolytic solution is 1M LiPF6 ∕ DMC:EC:DEC.
On the automatic detecting box of lithium-ion secondary cell, above-mentioned battery is carried out to electrochemical property test, content measurement comprises the capacity circulating conservation rate of the internal resistance of cell, 1C impulse electricity.Cyclic curve figure is shown in Fig. 3, and detected result is in 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 in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (5)
1. for a preparation method for the conductive agent of lithium ion battery, it is characterized in that: comprise the following steps:
(1) with the vitriol oil and potassium permanganate, natural flake graphite is oxidized to intercalation, is washed to neutrality, then at 60 DEG C～100 DEG C, dry, then at 800 DEG C～1000 DEG C expansion process 10～60 seconds, obtain expanded graphite; The expanding volume of processing the expanded graphite obtaining is 30mL ∕ g～300mL ∕ g; Median size≤10 μ the m of described natural flake graphite; The mass ratio of described natural flake graphite, the vitriol oil and potassium permanganate is 1:4～8:0.1～1; The concentration of the described vitriol oil is 90%～98%;
(2) expanded graphite is joined in the deionized water containing dispersion agent, then add mill ball, stirring ball-milling 60～300 minutes; Expanded graphite: dispersion agent: deionized water: the mass ratio of mill ball is 1:0.1～1:1～5:1～5; Described dispersion agent is one or more in polyvinyl alcohol, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, alcohol and sodium cellulose glycolate;
(3) slurry after grinding is sprayed and is dried, obtaining particle diameter is the submicron order conductive agent of 0.1 μ m～1 μ m.
2. the preparation method of a kind of conductive agent for lithium ion battery according to claim 1, is characterized in that: carbon content >=95% of natural flake graphite.
3. the preparation method of a kind of conductive agent for lithium ion battery according to claim 1, is characterized in that: the technique of step (1) expansion process is expansion process 40 seconds in the retort furnace of 900 DEG C of temperature.
4. the preparation method of a kind of conductive agent for lithium ion battery according to claim 1, is characterized in that: in step (3), the inlet temperature of spray-dired warm air is 200 DEG C～300 DEG C, and temperature out is 40 DEG C～90 DEG C.
5. the preparation method of a kind of conductive agent for lithium ion battery according to claim 1, is characterized in that: described mill ball is zirconia ball, and choosing sphere diameter specification is one or more the collocation uses in 2mm～40mm; The rotating speed of agitating ball mill used is that 30～300 Zhuan ∕ divide.
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| CN103387229B (en) * | 2013-07-23 | 2015-03-18 | 哈尔滨工业大学 | A preparation method for porous graphene and a preparation method for a graphene-based aluminium-air cell |
| 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 |
| 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 |
| CN104505515B (en) * | 2014-12-26 | 2016-11-30 | 广东东莞市天润电子材料有限公司 | A kind of ferrous phosphate lithium battery nano-graphite conductive agent and preparation method thereof |
| JP6988169B2 (en) * | 2017-05-26 | 2022-01-05 | トヨタ自動車株式会社 | A method for manufacturing a negative electrode for a non-aqueous electrolyte secondary battery, and a method for manufacturing a non-aqueous electrolyte secondary battery. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348251A (en) * | 2008-09-01 | 2009-01-21 | 武汉理工大学 | Method for preparing graphite nanosheet using high-energy ball mill |
| CN101997120A (en) * | 2010-10-09 | 2011-03-30 | 深圳市贝特瑞纳米科技有限公司 | Lithium ion battery conductive additive and preparation method thereof |
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