CN102610827B - Conductive additive for preparing power lithium ion battery cathode material and preparation method thereof - Google Patents
Conductive additive for preparing power lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000002482 conductive additive Substances 0.000 title claims abstract description 20
- 239000010406 cathode material Substances 0.000 title abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 127
- 239000010439 graphite Substances 0.000 claims abstract description 85
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 85
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 28
- 238000009830 intercalation Methods 0.000 claims description 24
- 230000002687 intercalation Effects 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 10
- 239000007772 electrode material Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- 230000003407 synthetizing effect Effects 0.000 abstract 1
- 241000238413 Octopus Species 0.000 description 14
- 239000006258 conductive agent Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229940097267 cobaltous chloride Drugs 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910014562 C—LiFePO4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NLAGNNORBYGNAV-UHFFFAOYSA-N isotriacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCC(C)C NLAGNNORBYGNAV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000012546 transfer Methods 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
Abstract
The invention provides a conductive additive for preparing power lithium ion battery cathode material and a preparation method of the conductive additive, the conductive additive is a composite of an expanded graphite and a carbon nano tube, one end of the carbon nano tube is located between expanded graphite layers, the other end is exposed outside the expanded graphite. The preparation method comprises the following steps: synthetizing the expanded graphite; interposing one or more of iron, nickel or cobalt between the expanded graphite layers; growing the carbon nano tube between the expanded graphite layers according to gaseous phase catalytic technology; at the last, removing metal impurities. The conductive additive of the invention can significantly improve low-temperature cycle performance and high-rate electrochemical performance of electrodes, can be dispersed and cannot be aggregated easily during electrode material mixing and pulping processes. According to the invention, the preparation method has the advantages of simple operation, easy industrialization application, low energy consumption and lower cost.
Description
Technical field
The present invention relates to a kind of preparation method of the additive for lithium ion battery negative material, be particularly applicable to the preparation method of conductive additive prepared by negative electrode of power lithium-ion battery material.
Background technology
Electrodes conduct agent is an important materials that affects electrode active material chemical property, especially aspect power lithium-ion battery, plays a part especially very crucially, even can directly determine in some cases the quality of performance of lithium ion battery.Thereby research and develop electrode conductive material and preparation method for high-end power lithium-ion battery, to promoting power lithium-ion battery development pole valuable.
In the charge and discharge process of lithium ion battery, have ion diffusion and electric charge transfer step, thereby electrode material must be the good mixed conductor of ion and electronics simultaneously.The conductivity of the positive electrode that current lithium ion battery is used is generally all 10
-1～10
-6s/cm, only depends on himself to conduct electricity and can not meet the requirement of high power charging-discharging far away, so need in active material, add conductive agent to improve conductivity.The negative pole of lithium ion battery mostly is the good graphite type material of conductivity, in low range charge and discharge process generally without adding conductive agent, but for power-type lithium ion battery, add a little conductive agent can reduce the contact resistance between negative active core-shell material, significantly weaken the ohmic polarization situation of electrode.Therefore conductive agent has very large impact to the performance of lithium ion battery.It is high that carbon nano-tube has degree of crystallinity, the performance that electric conductivity is good, there is again filamentary structure simultaneously, be conducive to form effective conductive network and fixed electrode material in electrode, in addition, its specific surface of this material is large, have loose structure, is easy to Electolyte-absorptive, is one of research and development key technology of current driving force lithium ion battery.Patent and document [Performance of carbon-fiber-containing LiFePO4cathodes for high-power applications, Thorat I V, JPS, 2006 (162): 673-678; Effect of carbon nanotube on the electrochemical performance of C-LiFePO4/graphite battery, Liu Y J, JPS, 2008 (184): 522-526; Zhang Qingtang. a kind of lithium ion secondary battery positive electrode, cathode material conductive agent and preparation method thereof, China, 1770515A[P] .2006-05-10.] all reported the performance of carbon nanotube conducting agent and composite material thereof, found that, the performance of carbon nanotube conducting agent is better than carbon black, gas-phase growth of carbon fibre and graphite microparticles.Yet, the draw ratio of carbon nano-tube is generally higher, very easily produces carbon nano-tube from the situation of reeling in the process of making electrode slice, is unfavorable for the dispersed of conductive agent and active particle, and the technique of synthetic less draw ratio carbon nano-tube is not bery ripe, within the short time, cannot realize industrialization.
Summary of the invention
The present invention aims to provide and a kind ofly improves with negative active core-shell material adhesion, reduces self agglomeration, improves electrode material performance, is easy to realize conductive additive and the preparation method prepared by negative electrode of power lithium-ion battery material that be applicable to of industrialization.
The present invention realizes by following scheme:
A kind of conductive additive for the preparation of negative electrode of power lithium-ion battery material, the composite material being formed by expanded graphite and carbon nano-tube, one end of carbon nano-tube is positioned at the interlayer of expanded graphite, the other end is exposed to outside expanded graphite, shape is similar to " octopus ", " octopus health " is expanded graphite, and " octopus peduncle " is carbon nano-tube.
For making conductive additive have more better performances, its preferred feature comprises: described carbon nano-tube is multilayer carbon nanotube, total caliber 0.5～3nm, and one end length being exposed to outside expanded graphite is 10～50 μ m; The graphite surface layer number of described expanded graphite is 20～50 layers, graphite face average-size 20～40 μ m, and graphite layers distance is 0.35～0.85nm.
The preparation method of above-mentioned conductive additive, comprises the steps:
(1) synthetic expanded graphite; This step be take graphite as raw material, adopts existing organic intercalation technical method to prepare.First graphite is mixed with perchloric acid powder (mass ratio 13～6:1), then under rapid stirring, join glacial acetic acid (with graphite ratio be 5g:6mL) in, continue to stir certain hour (10～30min), proceed in ball grinding stirring machine, rotating speed with 1000～5000rpm stirs 0.5～3h, ultrasonic processing 5～72h under 800～2000W power then, by the centrifugal expansible graphite that makes, then gained expansible graphite is prepared to expanded graphite in 850～1000 ℃ of heat treatment 0.5～2min under air atmosphere.
(2) one or more in fe, nickel or cobalt are inserted into expanded graphite interlayer; Can adopt existing metal intercalation method to prepare metal intercalation expanded graphite, also can adopt following solid phase intercalation technology to prepare: under 45～100 ℃ of conditions, one or more in anhydrous metal molysite, nickel salt or cobalt salt are mixed with the non-proton organic matter being in a liquid state, make the aaerosol solution of anhydrous metal salt, the expanded graphite more described (1) step being made joins in anhydrous metal salt suspensioning liquid, stir, standing 0～4h then, in 400～700 ℃ of isolated air heat treatments, be incubated 12～48h again.A kind of in 18～30 linear paraffin of the preferred paraffin wax of the non-proton organic matter of described liquid state or carbon number, paraffin wax is preferred molten paraffin wax or Valelinum Liquidum.Described slaine is that every 10ml organic substance mixes with 0.5～8g slaine with the mixed proportion of liquid state organics, and preferred proportion is that every 10ml organic substance mixes with 1.5～2.5g slaine.
(3) the metal intercalation expanded graphite (2) step being made, under 700～1300 ℃ of conditions, passes into hydrogen and small organic molecule, and constant temperature 1～12h is cooling afterwards.Small organic molecule is typically chosen in benzene, acetylene, toluene etc.
(4) remove the metal impurities in material.Method is: it is dry that metal intercalation expanded graphite-carbon nano tube compound material that (3) step is made is dipped in aqueous hydrochloric acid solution, and dip time is 30～90min, then washs---filtration---, obtains last additive material.
Compared with prior art, the present invention has following beneficial effect:
1. additive composite material of the present invention, is bound by one end of carbon nano-tube the interlayer of expanded graphite, forms " octopus " shape structure, can guarantee on the one hand the excellent conductive performance of carbon nano-tube, can avoid again on the other hand carbon nano-tube from agglomeration.
2. expanded graphite-the carbon nanotube composite conductive agent of the present invention this " octopus " shape, itself just can form good conductive network, the utilance that be conducive to weaken electrode polarization, increases active material.In addition, this structure also helps the adhesion that increases carbon nano-tube and active material, and carbon nano-tube can be wrapped in active particle around expanded graphite, makes active material be difficult for coming off from electrode, has strengthened the cycle life of electrode.
3. expanded graphite-carbon nanotube composite conductive agent of the present invention is compared with existing single-phase carbon nanotube conducting agent, at same LiFePO
4under technology for preparing electrode condition, the capacity that adds the former the electrode obtained during 0.1C multiplying power is 165mAh/g, and the capacity that adds the latter's the electrode obtained is 160mAh/g; Under 10C multiplying power, the capacity of two kinds of electrode materials is respectively 131mAh/g and 122mAh/g, 1000 capability retentions that circulate are respectively 92% and 87%, and capacity and the cycle life performance of the negative material that has added this additive of the present invention when high magnification promotes obviously.
4. expanded graphite-carbon nanotube composite conductive agent of the present invention is compared with existing single-phase carbon nanotube conducting agent, under same graphitized intermediate-phase carbon microballoon technology for preparing electrode condition, the capacity that adds the former the electrode obtained during 0.1C multiplying power is 324mAh/g, and the capacity that adds the latter's the electrode obtained is 326mAh/g; Under 30C multiplying power, the capacity of two kinds of electrode materials is respectively 311mAh/g and 293mAh/g, and 3000 capability retentions that circulate are respectively 95% and 90%.Capacity and the cycle life performance of the negative material that has added this additive of the present invention when high magnification promotes obviously.
5. preparation method of the present invention is the industrial gas phase catalytic processes easily realizing, preparation method's technique of lower draw ratio carbon nano-tube is more ripe, more easily realize industrialization, more can alleviate the market demand of low draw ratio carbon nano-tube, meet the application market demand of power lithium-ion battery.
Embodiment
embodiment 1
(1) prepare expanded graphite: 1000Kg graphite is mixed with 462g perchloric acid powder, then under rapid stirring, join in 1200mL glacial acetic acid, continue to stir 30min, proceed in ball grinding stirring machine, rotating speed with 1000～5000rpm stirs 3h, then ultrasonic processing 72h under 1800W power by the centrifugal expansible graphite that makes, then prepares expanded graphite in 900 ℃ of heat treatment 1min by gained expansible graphite under air atmosphere;
(2) metallic iron intercalation: at 60 ℃ of temperature, 250g anhydrous ferric chloride is mixed to the aaerosol solution that makes anhydrous ferric chloride with the paraffin of 1000mL melting, the expanded graphite of (1) step and iron chloride suspension agitation is even, standing 1h then, proceed to isolated air in tube furnace and be heat-treated to 600 ℃, after insulation 48h, obtain the expanded graphite of iron intercalation;
(3) the iron intercalation expanded graphite of upper step is warming up to 1100 ℃, passes into hydrogen and acetylene gaseous mixture that volume ratio is 1:1.2, constant temperature 8h, cooling afterwards, make iron intercalation expanded graphite-carbon nano tube compound material.
(4) it is that in 10% hydrochloric acid, dip time is 30min that the iron intercalation expanded graphite-carbon nano tube compound material upper step being made is dipped in concentration, then through washing---filtration---drying and other steps.
The conductive additive for the preparation of negative electrode of power lithium-ion battery material that adopts said method to prepare, the composite material being formed by expanded graphite and carbon nano-tube, one end of carbon nano-tube is positioned at the interlayer of expanded graphite, the other end is exposed to outside expanded graphite, shape is similar to " octopus ", " octopus health " is expanded graphite, and " octopus peduncle " is carbon nano-tube.Carbon nano-tube is multilayer carbon nanotube, and total caliber is 2.6nm, and one end length being exposed to outside expanded graphite is 43 μ m; The graphite surface layer number of expanded graphite is 21 layers, graphite face average-size 22 μ m, and graphite layers distance is 0.83nm.The conductivity of material is 631S/cm after tested.
embodiment 2
(1) prepare expanded graphite: 1000Kg graphite is mixed with 387g perchloric acid powder, then under rapid stirring, join in 1200mL glacial acetic acid, continue to stir 30min, proceed in ball grinding stirring machine, rotating speed with 5000rpm stirs 3h, then ultrasonic processing 72h under 1500W power by the centrifugal expansible graphite that makes, then prepares expanded graphite in 1000 ℃ of heat treatment 2min by gained expansible graphite under air atmosphere;
(2) metallic nickel intercalation: at 60 ℃ of temperature, 200g Dehydrated nickel chloride is mixed to the aaerosol solution that makes Dehydrated nickel chloride with the positive melissane of 1000mL melting, the expanded graphite of (1) step and nickel chloride suspension agitation is even, standing 2h then, proceed to isolated air in tube furnace and be heat-treated to 500 ℃, after insulation 20h, obtain the expanded graphite of nickel intercalation;
(3) the nickel intercalation expanded graphite upper step being made is warming up to 1100 ℃, passes into hydrogen and toluene gaseous mixture that volume ratio is 5:1.8, and constant temperature 8h is cooling afterwards, makes nickel intercalation expanded graphite-carbon nano tube compound material;
(4) the nickel intercalation expanded graphite-carbon nano tube compound material of upper step being dipped in to concentration is that in 10% hydrochloric acid, dip time is 60min, then through washing, filtration, drying and other steps.
The conductive additive for the preparation of negative electrode of power lithium-ion battery material that adopts said method to prepare, the composite material being formed by expanded graphite and carbon nano-tube, one end of carbon nano-tube is positioned at the interlayer of expanded graphite, the other end is exposed to outside expanded graphite, shape is similar to " octopus ", " octopus health " is expanded graphite, and " octopus peduncle " is carbon nano-tube.Total caliber is 2.1nm, and one end length being exposed to outside expanded graphite is 44 μ m; The graphite surface layer number of expanded graphite is 26 layers, graphite face average-size 27 μ m, and graphite layers distance is 0.67nm.The conductivity of material is 793S/cm after tested.
embodiment 3
(1) prepare expanded graphite: 1000Kg graphite is mixed with 80g perchloric acid powder, then under rapid stirring, join in 1200mL glacial acetic acid, continue to stir 10min, proceed in ball grinding stirring machine, rotating speed with 3500rpm stirs 3h, then ultrasonic processing 72h under 1800W power by the centrifugal expansible graphite that makes, then prepares expanded graphite in 1100 ℃ of heat treatment 2min by gained expansible graphite under air atmosphere;
(2) metallic nickel cobalt intercalation: at 60 ℃ of temperature, the Dehydrated nickel chloride and the waterless cobaltous chloride that amount to 150g are mixed to the aaerosol solution that makes Dehydrated nickel chloride and waterless cobaltous chloride with the n-octadecane of 1000mL melting, the expanded graphite of (1) step and above-mentioned suspension agitation is even, standing 1h then, proceed to isolated air in tube furnace and be heat-treated to 700 ℃, after insulation 36h, obtain the expanded graphite of metallic nickel and cobalt intercalation;
(3) again the metallic nickel of upper step and cobalt intercalation expanded graphite are warming up to 1100 ℃, passing into volume ratio is the hydrogen of 5:1.5 and the gaseous mixture of benzene, and constant temperature 2h is cooling afterwards, makes nickel cobalt intercalation expanded graphite-carbon nano tube compound material;
(4) the nickel cobalt intercalation expanded graphite-carbon nano tube compound material of upper step being dipped in to concentration is that in 10% hydrochloric acid, dip time is 90min, then through washing, filtration, drying and other steps.
The conductive additive for the preparation of negative electrode of power lithium-ion battery material that adopts said method to prepare, the composite material being formed by expanded graphite and carbon nano-tube, one end of carbon nano-tube is positioned at the interlayer of expanded graphite, the other end is exposed to outside expanded graphite, shape is similar to " octopus ", " octopus health " is expanded graphite, and " octopus peduncle " is carbon nano-tube.Total caliber is 1.9nm, and one end length being exposed to outside expanded graphite is 12 μ m; The graphite surface layer number of expanded graphite is 45 layers, graphite face average-size 37 μ m, and graphite layers distance is 0.48nm.The conductivity of material is 597S/cm after tested.
Claims (6)
1. for the preparation of a preparation method for the conductive additive of negative electrode of power lithium-ion battery material, it is characterized in that: comprise the steps that (1) synthesize expanded graphite; (2) under 45 ℃～100 ℃ conditions, one or more in anhydrous metal molysite, nickel salt or cobalt salt are mixed with the non-proton organic matter being in a liquid state, make the suspension of anhydrous metal salt, the expanded graphite more described (1) step being made joins in anhydrous metal salt suspensioning liquid, stir, standing 0～4h then, then in 400～700 ℃ of isolated air heat treatments, insulation 12～48h; (3) the metal intercalation expanded graphite (2) step being made, under 700～1300 ℃ of conditions, passes into hydrogen and small organic molecule, and constant temperature 1～12h is cooling afterwards; (4) remove metal.
2. the preparation method who prepares conductive additive as claimed in claim 1, is characterized in that: a kind of in 18～30 linear paraffin of the preferred paraffin wax of the non-proton organic matter of described liquid state or carbon number.
3. the preparation method who prepares conductive additive as claimed in claim 1 or 2, is characterized in that: described slaine is that every 10ml organic substance mixes with 0.5～8g slaine with the mixed proportion of liquid state organics.
4. the preparation method who prepares conductive additive as claimed in claim 3, is characterized in that: described slaine mixes with 1.5～2.5g slaine with the preferred every 10ml organic substance of mixed proportion of liquid state organics.
5. the preparation method who prepares conductive additive as claimed in claim 1 or 2, it is characterized in that: the method that described (4) step is removed metal is preferably, metal intercalation expanded graphite-carbon nano tube compound material that (3) step is made is dipped in aqueous hydrochloric acid solution, it is dry that dip time is 30～90min, then washs---filtration---.
6. the preparation method who prepares conductive additive as claimed in claim 4, it is characterized in that: the method that described (4) step is removed metal is preferably, metal intercalation expanded graphite-carbon nano tube compound material that (3) step is made is dipped in aqueous hydrochloric acid solution, it is dry that dip time is 30～90min, then washs---filtration---.
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| CN107706391B (en) * | 2017-10-16 | 2020-06-02 | 常州大学 | Carbon-based composite material of low-temperature lithium ion battery and preparation method thereof |
| CN108878893B (en) * | 2018-06-29 | 2021-08-17 | 桑顿新能源科技(长沙)有限公司 | Modified current collector for negative electrode of quick-charging lithium ion battery and preparation method thereof |
| CN114976085A (en) * | 2022-03-29 | 2022-08-30 | 广东氢发新材料科技有限公司 | Vapor deposition carbon nanofiber network modified graphite composite bipolar plate and preparation method thereof |
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|---|---|---|---|---|
| EP1059266A3 (en) * | 1999-06-11 | 2000-12-20 | Iljin Nanotech Co., Ltd. | Mass synthesis method of high purity carbon nanotubes vertically aligned over large-size substrate using thermal chemical vapor deposition |
| CN1699620A (en) * | 2004-05-21 | 2005-11-23 | 龚平 | Process for preparing a catalyst for synthesis of carbon nano tube |
| CN100569509C (en) * | 2007-06-15 | 2009-12-16 | 清华大学 | A kind of carbon nano pipe array/laminated composite and preparation method thereof |
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2012
- 2012-03-28 CN CN201210086713.5A patent/CN102610827B/en active Active
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