CN102610827A - 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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- CN102610827A CN102610827A CN2012100867135A CN201210086713A CN102610827A CN 102610827 A CN102610827 A CN 102610827A CN 2012100867135 A CN2012100867135 A CN 2012100867135A CN 201210086713 A CN201210086713 A CN 201210086713A CN 102610827 A CN102610827 A CN 102610827A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 239000002482 conductive additive Substances 0.000 title claims abstract description 24
- 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 107
- 239000010439 graphite Substances 0.000 claims abstract description 93
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 93
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 22
- 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 16
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 31
- 238000009830 intercalation Methods 0.000 claims description 24
- 230000002687 intercalation Effects 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011229 interlayer Substances 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 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
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- 238000001816 cooling 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
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007772 electrode material Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 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
- 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
- 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
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 238000012360 testing method Methods 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
- 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
- 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 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
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 230000003313 weakening effect Effects 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
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- Battery Electrode And Active Subsutance (AREA)
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 additive and preparation method who is used for lithium ion battery negative material, particularly be applicable to the conductive additive and the preparation method of power lithium-ion battery negative material preparation.
Background technology
The electrodes conduct agent is an important materials that influences the electrode active material chemical property, especially aspect power lithium-ion battery, play a part especially very crucial, in some cases even can directly determine the quality of lithium ion battery performance.Thereby research and develop high-end power lithium-ion battery with electrode conductive material and preparation method, to promoting the power lithium-ion battery development pole valuable.
Have ions diffusion and electric charge transfer step in the charge and discharge process of lithium ion battery simultaneously, thereby electrode material must be the well-mixed conductor of ion and electronics.The conductivity of the positive electrode that present lithium ion battery is used is generally all 10
-1～10
-6S/cm only depends on himself to conduct electricity and has satisfied not the requirement of high power charging-discharging far away, and therefore need in active material, add conductive agent improves conductivity.Mostly the negative pole of lithium ion battery is the graphite type material that conductivity is good; In the low range charge and discharge process, generally need not to add conductive agent; But for power-type lithium ion battery; Add a little conductive agent and can reduce the contact resistance between negative active core-shell material, significantly weaken the ohmic polarization situation of electrode.Therefore conductive agent has very big influence to the performance of lithium ion battery.CNT has the degree of crystallinity height; The performance that electric conductivity is good has filamentary structure again simultaneously, helps in electrode, forming effective conductive network and fixed electrode material; In addition; Its specific surface of this material is big, have loose structure, is easy to Electolyte-absorptive, is one of research and development key technology of current driving force lithium ion battery.Document and patent [Thorat I V, JPS, 2006 (162): 673-678; 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 carbon nanotube conducting agent and performance of composites thereof; The result finds 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 CNT is generally higher, in the process of making electrode slice, very easily produces CNT from the situation of reeling, and is unfavorable for the even dispersion of conductive agent and active particle; And the technology of synthetic less draw ratio CNT is not really ripe, can't realize industrialization within the short time.
Summary of the invention
This has to aim to provide and a kind ofly improves with the negative active core-shell material adhesion, reduces self agglomeration, improves the electrode material performance, is easy to realize the conductive additive and the preparation method that are applicable to the preparation of power lithium-ion battery negative material of industrialization.
The present invention realizes through following scheme:
A kind of conductive additive that is used to prepare the power lithium-ion battery negative material; The composite material that forms by expanded graphite and CNT; One end of CNT is positioned at the interlayer of expanded graphite, and the other end is exposed to outside the expanded graphite, and shape is similar to " octopus "; " octopus health " is expanded graphite, and " octopus peduncle " is CNT.
For making conductive additive have more better performances, its preferable feature comprises: said CNT is a multilayer carbon nanotube, total caliber 0.5～3nm, and being exposed to the outer end length of expanded graphite is 10～50 μ m; The graphite surface layer number of said expanded graphite is 20～50 layers, graphite face average-size 20～40 μ m, and the 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 is a raw material with graphite, adopts existing organic substance intercalation technique method to prepare.At first graphite and perchloric acid powder are mixed (mass ratio 13～6: 1); Join under then stirring fast glacial acetic acid (with the graphite ratio be 5g: 6mL); Continue to stir certain hour (10～30min); Change in the ball milling mixer, with rotating speed stirring 0.5～3h, then the sonicated 5～72h under 800～2000W power of 1000～5000rpm; Through the centrifugal expansible graphite that makes, again the gained expansible graphite is prepared expanded graphite in 850～1000 ℃ of heat treatment 0.5～2min under air atmosphere.
(2) in fe, nickel or the cobalt one or more are inserted into the expanded graphite interlayer; Can adopt existing metal intercalation method to prepare metal intercalation expanded graphite; Also can adopt following solid phase intercalation technique to prepare: under 45～100 ℃ of conditions; In anhydrous metal molysite, nickel salt or the cobalt salt one or more are mixed with the aprotic organic substance that is in a liquid state, make the aaerosol solution of anhydrous metal salt, the expanded graphite that more said (1) step is made joins in the anhydrous metal salt suspensioning liquid; Stir; Then leave standstill 0～4h, again in 400～700 ℃ of secluding air heat treatments, insulation 12～48h.A kind of in 18～30 linear paraffin of described preferred paraffin wax of liquid aprotic organic substance or carbon number, paraffin wax is preferred molten paraffin wax or Valelinum Liquidum then.Said 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) with (2) the metal intercalation expanded graphite that makes of step under 700～1300 ℃ of conditions, feed hydrogen and small organic molecule, constant temperature 1～12h, cooling afterwards.Small organic molecule is typically chosen in benzene, acetylene, toluene etc.
(4) remove metal impurities in the material.Method is: metal intercalation expanded graphite-carbon nano tube compound material that (3) step was made is dipped in the aqueous hydrochloric acid solution, and dip time is 30～90min, and washing---filtration---drying gets additive material to the end again.
Compared with prior art, the present invention has following beneficial effect:
1. additive composite material of the present invention is bound by the interlayer of expanded graphite with an end of CNT, forms " octopus " shape structure, can guarantee the excellent conductive performance of CNT on the one hand, can avoid again on the other hand CNT from agglomeration.
2. expanded graphite-the carbon nanotube composite conductive agent of the present invention this " octopus " shape, itself just can form the favorable conductive network, the utilance that help weakening electrode polarization, increases active material.In addition, this structure also helps the adhesion that increases CNT and active material, and CNT can be wrapped in active particle around the expanded graphite, makes that active material is difficult to come 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 the technology for preparing electrode condition, the capacity that adds the former gained electrode during the 0.1C multiplying power is 165mAh/g, and the capacity that adds latter's gained electrode is 160mAh/g; The capacity of the following two kinds of electrode materials of 10C multiplying power 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 negative material when high magnification that has added this additive of the present invention 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 graphitization MCMB technology for preparing electrode condition; 0.1C adding the capacity of the former gained electrode during multiplying power is 324mAh/g, the capacity that adds latter's gained electrode is 326mAh/g; The capacity of the following two kinds of electrode materials of 30C multiplying power 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 negative material when high magnification that has added this additive of the present invention promotes obviously.
5. preparation method of the present invention is that the gas phase catalytic processes that is prone to realization is gone up in industry; Preparation method's technology of low draw ratio CNT is ripe; More be prone to realize industrialization, more can alleviate the market demand of low draw ratio CNT, satisfy the application market demand of power lithium-ion battery.
Embodiment
Embodiment 1
(1) preparation expanded graphite: 1000Kg graphite and 462g perchloric acid powder are mixed; Join in the 1200mL glacial acetic acid under then stirring fast, continue to stir 30min, change in the ball milling mixer; Rotating speed with 1000～5000rpm stirs 3h; Then sonicated 72h under 1800W power through the centrifugal expansible graphite that makes, prepares expanded graphite in 900 ℃ of heat treatment 1min with the gained expansible graphite again under air atmosphere;
(2) metallic iron intercalation: the paraffin with 250g anhydrous ferric chloride and 1000mL fusion under 60 ℃ of temperature mixes the aaerosol solution that makes anhydrous ferric chloride; The expanded graphite and the iron chloride suspension in (1) step are stirred; Then leave standstill 1h; Change the interior secluding air of tube furnace over to and be heat-treated to 600 ℃, obtain the expanded graphite of iron intercalation behind the insulation 48h;
(3) will go up the iron intercalation expanded graphite in step and be warming up to 1100 ℃, the feeding volume ratio is 1: 1.2 hydrogen and an acetylene gaseous mixture, constant temperature 8h, and cooling makes iron intercalation expanded graphite-carbon nano tube compound material afterwards.
(4) will going up iron intercalation expanded graphite-carbon nano tube compound material of making of step, to be dipped in concentration be that dip time is 30min, again through washing---filtration---drying and other steps in 10% the hydrochloric acid.
The conductive additive that is used to prepare the power lithium-ion battery negative material that adopts method for preparing to obtain; The composite material that forms by expanded graphite and CNT; One end of CNT is positioned at the interlayer of expanded graphite, and the other end is exposed to outside the expanded graphite, and shape is similar to " octopus "; " octopus health " is expanded graphite, and " octopus peduncle " is CNT.CNT is a multilayer carbon nanotube, and total caliber is 2.6nm, and being exposed to the outer end length of 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 the graphite layers distance is 0.83nm.Conductivity through test material is 631S/cm.
Embodiment 2
(1) preparation expanded graphite: 1000Kg graphite and 387g perchloric acid powder are mixed; Join in the 1200mL glacial acetic acid under then stirring fast, continue to stir 30min, change in the ball milling mixer; Rotating speed with 5000rpm stirs 3h; Then sonicated 72h under 1500W power through the centrifugal expansible graphite that makes, prepares expanded graphite in 1000 ℃ of heat treatment 2min with the gained expansible graphite again under air atmosphere;
(2) metallic nickel intercalation: the positive melissane with 200g anhydrous chlorides of rase nickel and 1000mL fusion under 60 ℃ of temperature mixes the aaerosol solution that makes anhydrous chlorides of rase nickel; The expanded graphite and the nickel chloride suspension in (1) step are stirred; Then leave standstill 2h; Change the interior secluding air of tube furnace over to and be heat-treated to 500 ℃, obtain the expanded graphite of nickel intercalation behind the insulation 20h;
(3) will go up the nickel intercalation expanded graphite that makes of step and be warming up to 1100 ℃, and feed volume ratio and be 5: 1.8 hydrogen and toluene gaseous mixture, constant temperature 8h cools off afterwards, makes nickel intercalation expanded graphite-carbon nano tube compound material;
(4) it is that dip time is 60min, again through washing, filtration, drying and other steps in 10% the hydrochloric acid that the nickel intercalation expanded graphite-carbon nano tube compound material that will go up the step is dipped in concentration.
The conductive additive that is used to prepare the power lithium-ion battery negative material that adopts method for preparing to obtain; The composite material that forms by expanded graphite and CNT; One end of CNT is positioned at the interlayer of expanded graphite, and the other end is exposed to outside the expanded graphite, and shape is similar to " octopus "; " octopus health " is expanded graphite, and " octopus peduncle " is CNT.Total caliber is 2.1nm, and being exposed to the outer end length of 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 the graphite layers distance is 0.67nm.Conductivity through test material is 793S/cm.
Embodiment 3
(1) preparation expanded graphite: 1000Kg graphite and 80g perchloric acid powder are mixed; Join in the 1200mL glacial acetic acid under then stirring fast, continue to stir 10min, change in the ball milling mixer; Rotating speed with 3500rpm stirs 3h; Then sonicated 72h under 1800W power through the centrifugal expansible graphite that makes, prepares expanded graphite in 1100 ℃ of heat treatment 2min with the gained expansible graphite again under air atmosphere;
(2) metallic nickel cobalt intercalation: will amount to the anhydrous chlorides of rase nickel of 150g under 60 ℃ of temperature and the n-octadecane of waterless cobaltous chloride and 1000mL fusion mixes the aaerosol solution that makes anhydrous chlorides of rase nickel and waterless cobaltous chloride; The expanded graphite and the above-mentioned suspension in (1) step are stirred; Then leave standstill 1h; Change the interior secluding air of tube furnace over to and be heat-treated to 700 ℃, obtain the expanded graphite of metallic nickel and cobalt intercalation behind the insulation 36h;
(3) will go up the metallic nickel and the cobalt intercalation expanded graphite in step again and be warming up to 1100 ℃, feeding volume ratio is 5: 1.5 the hydrogen and the gaseous mixture of benzene, constant temperature 2h, and cooling makes nickel cobalt intercalation expanded graphite-carbon nano tube compound material afterwards;
(4) it is that dip time is 90min, again through washing, filtration, drying and other steps in 10% the hydrochloric acid that the nickel cobalt intercalation expanded graphite-carbon nano tube compound material that will go up the step is dipped in concentration.
The conductive additive that is used to prepare the power lithium-ion battery negative material that adopts method for preparing to obtain; The composite material that forms by expanded graphite and CNT; One end of CNT is positioned at the interlayer of expanded graphite, and the other end is exposed to outside the expanded graphite, and shape is similar to " octopus "; " octopus health " is expanded graphite, and " octopus peduncle " is CNT.Total caliber is 1.9nm, and being exposed to the outer end length of 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 the graphite layers distance is 0.48nm.Conductivity through test material is 597S/cm.
Claims (10)
1. conductive additive that is used to prepare the power lithium-ion battery negative material; It is characterized in that: the composite material that forms by expanded graphite and CNT; One end of wherein said CNT is positioned at the interlayer of expanded graphite, and the other end is exposed to outside the expanded graphite.
2. the conductive additive that is used to prepare the power lithium-ion battery negative material as claimed in claim 1 is characterized in that: said CNT is a multilayer carbon nanotube, and total caliber is 0.5～3nm, and being exposed to the outer end length of expanded graphite is 10～50 μ m.
3. the conductive additive that is used to prepare the power lithium-ion battery negative material as claimed in claim 1 is characterized in that: the graphite surface layer number of said expanded graphite is 20～50 layers, graphite face average-size 20～40 μ m, and the graphite layers distance is 0.35～0.85nm.
4. one kind like the described preparation method who is used to prepare the conductive additive of power lithium-ion battery negative material of one of claim 1～3, it is characterized in that: comprise the steps that (1) synthesize expanded graphite; (2) in fe, nickel or the cobalt one or more are inserted into the expanded graphite interlayer; (3) with (2) the metal intercalation expanded graphite that makes of step under 700～1300 ℃ of conditions, feed hydrogen and small organic molecule, constant temperature 1～12h, cooling afterwards; (4) remove metal.
5. the preparation method of conductive additive as claimed in claim 4; It is characterized in that: the process in said (2) step is preferably: under 45 ℃～100 ℃ conditions; In anhydrous metal molysite, nickel salt or the cobalt salt one or more are mixed with the aprotic organic substance that is in a liquid state, make the suspension of anhydrous metal salt, the expanded graphite that more said (1) step is made joins in the anhydrous metal salt suspensioning liquid; Stir; Then leave standstill 0～4h, again in 400～700 ℃ of secluding air heat treatments, insulation 12～48h.
6. the preparation method of preparation conductive additive as claimed in claim 5 is characterized in that: a kind of in 18～30 linear paraffin of described preferred paraffin wax of liquid aprotic organic substance or carbon number.
7. like the preparation method of the described preparation conductive additive of one of claim 4～6, it is characterized in that: said slaine is that every 10ml organic substance mixes with 0.5～8g slaine with the mixed proportion of liquid state organics.
8. the preparation method of preparation conductive additive as claimed in claim 7 is characterized in that: said slaine mixes with 1.5～2.5g slaine with the preferred every 10ml organic substance of the mixed proportion of liquid state organics.
9. like the preparation method of the described preparation conductive additive of one of claim 4～6; It is characterized in that: (4) the step method of removing metal be preferably; Metal intercalation expanded graphite-carbon nano tube compound material that (3) step was made is dipped in the aqueous hydrochloric acid solution; Dip time is 30～90min, again washing---filtration---drying.
10. the preparation method of preparation conductive additive as claimed in claim 8; It is characterized in that: (4) the step method of removing metal be preferably; Metal intercalation expanded graphite-carbon nano tube compound material that (3) step was made is dipped in the aqueous hydrochloric acid solution; Dip time is 30～90min, again washing---filtration---drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706391A (en) * | 2017-10-16 | 2018-02-16 | 常州大学 | A kind of C-base composte material of low-temperature lithium ion battery and preparation method thereof |
| CN108878893A (en) * | 2018-06-29 | 2018-11-23 | 桑顿新能源科技有限公司 | A kind of fast charge negative electrode of lithium ion battery modified collector 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706391A (en) * | 2017-10-16 | 2018-02-16 | 常州大学 | A kind of C-base composte material of low-temperature lithium ion battery and preparation method thereof |
| 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 |
| CN108878893A (en) * | 2018-06-29 | 2018-11-23 | 桑顿新能源科技有限公司 | A kind of fast charge negative electrode of lithium ion battery modified collector 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102610827B (en) | 2014-09-17 |
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