CN101017893B - A tin carbon compound electrode material for lithium ion battery cathode and preparing method - Google Patents
A tin carbon compound electrode material for lithium ion battery cathode and preparing method Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 25
- 239000007772 electrode material Substances 0.000 title claims description 24
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 title claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 9
- 239000000463 material Substances 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000010439 graphite Substances 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 41
- 229910052744 lithium Inorganic materials 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000011232 storage material Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000007770 graphite material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000008188 pellet Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 8
- 229910021382 natural graphite Inorganic materials 0.000 claims description 8
- 239000011300 coal pitch Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010671 solid-state reaction Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- 229910020836 Sn-Ag Inorganic materials 0.000 claims description 3
- 229910020888 Sn-Cu Inorganic materials 0.000 claims description 3
- 229910020938 Sn-Ni Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910020988 Sn—Ag Inorganic materials 0.000 claims description 3
- 229910019204 Sn—Cu Inorganic materials 0.000 claims description 3
- 229910008937 Sn—Ni Inorganic materials 0.000 claims description 3
- 238000007908 dry granulation Methods 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 229910020944 Sn-Mg Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011149 active material Substances 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 239000002733 tin-carbon composite material Substances 0.000 abstract description 4
- 238000005253 cladding Methods 0.000 abstract 2
- 239000000047 product Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 57
- 229910052718 tin Inorganic materials 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 230000004087 circulation Effects 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 13
- -1 polytetrafluoroethylene Polymers 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910018727 Sn—Ag—C Inorganic materials 0.000 description 4
- 229910019189 Sn—Cu—C Inorganic materials 0.000 description 4
- 229910008892 Sn—Mg—C Inorganic materials 0.000 description 4
- 229910009007 Sn—Ni—C Inorganic materials 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000011366 tin-based material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 229910018725 Sn—Al Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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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 disclosed preparation method for Sn-C composite material for negative electrode of Li-ion cell comprises: (1) ball grinding the graphite and doped stannum salt material together; (2) adding product in (1) into alkali solution for reacting, filtering, and drying; (3) preparing the organic solution for cladding carbon layer, adding the product from last step, and drying for granulation; and (4) taking high-temperature solid phase reaction. The final product comprises the graphite body, cladding carbon layer and Sn-constained Li-storing material between the graphite surface and carbon layer, or in graphite layers, or in carbon layers. This invention can reduce the volume effect of Sn-constained active material, has well reversible specific capacity and cycle life.
Description
Technical field
The present invention relates to electrode material of a kind of lithium ion battery and preparation method thereof, particularly relate to a kind of tin carbon compound electrode material and this kind preparation methods of used as negative electrode of Li-ion battery.
Background technology
Extensive use and fast development along with various portable electric appts and electric automobile, people are also more and more higher to the demand and the performance requirement of all kinds of electric product power supplys, lithium rechargeable battery with superior combination property such as its high power characteristic in success over past ten years and be widely used in the mobile electronic terminal apparatus field.
Adopt lithium transition-metal oxide/graphite system at present in the commercialization lithium rechargeable battery mostly, because the theoretical lithium storage content of negative pole itself is lower in this battery system, the simple process modification of passing through is difficult to satisfy people's demand more and more higher to battery capacity, therefore seeks the focus that the higher negative material of capacity becomes negative material research; Negative material is discovered as Sn, Si, Al, Sb etc. can have the theoretical capacity that is far longer than graphite with the metal or alloy material that lithium forms alloy, has caused the extensive concern of battery material circle.But such material has very big bulk effect, causes the unsteadiness of material material structure in charge and discharge process to strengthen, material efflorescence and then cause the security performance problem.
Sn base negative material is owing to have very high theory gram specific capacity and volume and capacity ratio, and low embedding lithium current potential has higher stability and attracts tremendous attention than other metal_based materials.But tin-based material is the same with other metal_based materials, and tin-based material exists serious bulk effect in the process of removal lithium embedded, causes the cyclical stability variation of electrode, and material is easily efflorescence in the electrochemistry cyclic process, causes serious potential safety hazard.People such as M.Y.MA adopt the SnO of Preparation by Uniform Precipitation
2-graphite composite powder has the higher lithium of embedding first capacity, coulombic efficiency is very low but it circulates first, capacity attenuation is fast, this method not can solve bulk effect (The Chinese Journal ofNonferrous Metals, the Vol.15No.5 (2005): 793-798) of tin-based material in the removal lithium embedded process.Employing organic solution liquid impregnation-low-temperature carbonization methods such as Y.Liu have prepared advanced Sn/C composite material, the Sn/C composite material of this method preparation has the higher lithium of embedding first capacity, and its coulombic efficiency increasing of circulating first than last example, maximum can reach 84%, though the raising of tin content can increase the lithium storage content of material, but the capacity attenuation of this material is accelerated along with the increase of tin content, this has influenced the utilance of material to a great extent, cause the wasting of resources (Journal of Applied Electrochemistry, 32:687-692,2002).
Summary of the invention
Purpose of the present invention is exactly in order to overcome the above problems, and the tin carbon compound electrode material that is used for the lithium rechargeable battery negative pole and this preparation methods of a kind of height ratio capacity, stable cycle performance is provided.
For achieving the above object, the present invention has adopted following technical scheme:
The invention discloses a kind of tin carbon compound electrode material for lithium ion battery cathode, described combination electrode material comprises graphite body, coats carbon-coating and stanniferous class lithium storage materials, described stanniferous class lithium storage materials circle in graphite surface with coat between the carbon-coating or the boundary in the interlayer of graphite or the interlayer of coating carbon-coating.
Described stanniferous class lithium storage materials comprises the compound of tin or tin.
The compound of described tin comprises the oxide of tin or the alloy of tin.Preferably, the oxide of described tin is SnO
2, the alloy of described tin is Sn-Ag alloy, Sn-Mg alloy, Sn-Ni alloy or Sn-Cu alloy.
The content of described stanniferous class lithium storage materials in combination electrode material is 5%～60% (wt).
The thickness of described coating carbon-coating is 0.01 μ m～1 μ m.
The invention also discloses the preparation method of above-mentioned tin carbon compound electrode material, described method comprises step:
(1) graphite material is carried out ball milling with mixing up pink salt;
(2) react in the mixture adding aqueous slkali that step (1) is obtained, afterwards filtering drying;
(3) organic solution of preparation carbon coated layer material, and add the product that step (2) obtains therein, react back oven dry granulation;
(4) the granulated high temperature solid state reaction that carries out that step (3) is obtained.
Preferably, described method further comprises step (5) afterwards in step (4): reduce to room temperature naturally after high temperature solid state reaction finishes and obtain tin carbon compound electrode material.
In the combination electrode material for preparing, the content of described stanniferous class lithium storage materials is 5%～60% (wt), and the thickness of described coating carbon-coating is 0.01 μ m～1 μ m.
Described graphite material comprises natural flake graphite, spherical natural graphite or Delanium, describedly mixes up the mixture that pink salt comprises pink salt or pink salt and other slaines.
Preferably, described pink salt is SnCl
4, described other slaines comprise AgNO
3, MgCl
2, Ni (NO
3)
2Or CuCl
2
Described step (1) specifically is meant, with graphite material with mixing up pink salt and pellet places hermetically sealed can, and on planetary ball mill, carry out ball milling, the weight ratio of described pellet and graphite material is 0.5: 1～10: 1, the rotating speed of described ball milling is 20r/min～600r/min, and the time of described ball milling is 0.5 hour～100 hours.
Described step (2) specifically is meant, the mixture behind the ball milling is slowly added in the aqueous slkali, constantly stir in the time of adding, and at 20 ℃～100 ℃ following reaction filtering dryings after 0.5～100 hour, the pH value of described aqueous slkali is 7.5～13.
Preferably, described aqueous slkali is NaOH solution, KOH solution, NH
4OH solution or Ca (OH)
2Solution.
Described step (3) specifically is meant, compound concentration is the organic solution of the carbon coated layer material of 3%～7% (wt), under continuous condition of stirring, add the product that step (2) obtains, reacted 0.5～100 hour, constantly stir dry out solvent afterwards, continuous stirring-granulating in drying course in the course of reaction.
Preferably, the solvent of the organic solution of described carbon coated layer material is one or more in pyridine, acetone, oxolane, the ethanol, the preferred medium temperature coal pitch of described carbon coated layer material, and the organic solution concentration of being prepared is 5% (wt).
Described step (4) specifically is meant, the granulated good reaction vessel of air-tightness that places that step (3) is obtained heats up in 400～1600 ℃ with the heating rate of 2～30 ℃/min under protective atmosphere and carries out high temperature solid state reaction, and is incubated 10～240 minutes.
More specifically; described step (4) is meant; the granulated good reaction vessel of air-tightness that places that step (3) is obtained; heating rate with 3～15 ℃/min under protective atmosphere heats up in 400～600 ℃; and be incubated 10～240 minutes, heat up in 800～1600 ℃ with the heating rate of 7～30 ℃/min more afterwards, and be incubated 10～240 minutes; described protective atmosphere comprises protective gas and reducibility gas, and the volume content of described reducibility gas is 0～20%.Preferably, described protective gas comprises that a kind of in nitrogen, argon gas, helium, neon or the carbon dioxide, described reducibility gas comprise a kind of in hydrogen or the carbon monoxide.
Because adopted above scheme, the tin carbon compound electrode material that the present invention is prepared possesses following advantage is arranged:
1, tin carbon composite of the present invention, the mode of employing shell volume compensation can obviously alleviate the serious bulk effect that the stanniferous active material produces when removal lithium embedded;
2, the tin carbon composite prepared of the present invention has higher reversible specific capacity and long cycle life, and the initial charge capacity reaches 590mAh/g, and discharge capacity reaches 490mAh/g first, the capacity attenuation rate of 20 each circulations in circulation back only 0.5%;
3, the tin carbon composite prepared of the present invention, but its doff lithium current potential is higher than ion secondary battery cathode material lithiums commonly used such as graphite-like, thus can prevent that lithium metal the separating out of negative terminal surface, is convenient to high rate charge-discharge.
Embodiment
The present invention is directed to tin and when removal lithium embedded, produce serious bulk effect, adopt the mode of shell volume compensation, the composite material for preparing a kind of stanniferous, the height ratio capacity characteristic that keeps tin, make the change in volume of overall electrode be controlled at reasonable levels simultaneously, increase the Stability Analysis of Structures of electrode in the battery cyclic process.
In the tin carbon compound electrode material that is used for the lithium rechargeable battery negative pole provided by the invention, the graphite material with higher capacity is present among the shell of composite material as the main body of composite material; In the main body graphite surface and coat between the carbon-coating, perhaps the boundary is in the interlayer of graphite or coat the interlayer of carbon-coating as main active substances circle for stanniferous class lithium storage materials with high power capacity; Have the coating layer of the carbon coated class material of certain lithium storage content, reversible removal lithium embedded stable performance as composite material.
The main body of combination electrode material is a graphite material, comprises various graphite-like material with carbon elements such as natural flake graphite, spherical natural graphite, Delanium.
Stanniferous class lithium storage materials comprises tin as main active substances, or the oxide S nO of tin or SnO
2, or the alloy of tin, as Sn-Ag, Sn-Al, Sn-Ni, Sn-Cu etc., perhaps other compound of tin; Tin class material can be present in before cracking reaction in the composite material, also can form in cracking reaction.
Have the coating layer of the carbon coated class material of certain lithium storage content, reversible removal lithium embedded stable performance, be meant the coating layer predecessor, form material with carbon element after the part graphitization with certain lithium storage content by reactions such as cracking dehydrogenation oxygen under the high temperature as composite material.The multiple material with carbon element predecessor that can select for use in the practical application, such as coal tar pitch, petroleum asphalt, phenolic resins, epoxy resin, polymethyl methacrylate, polytetrafluoroethylene etc., and can be according to the suitable consumption of different choice of the carbonization yield of these material with carbon element presomas.The carbon-coating variable thickness sample that different material with carbon element predecessors generates, its one-tenth-value thickness 1/10 is usually between 0.01 μ m～1 μ m.
But the lithium storage content of composite material is regulated by the content of stanniferous class active material in composite material.Specifically be meant, the cycle performance of comprehensive negative material and capacity performance, by the ratio of the main body graphite before and after the control cracking reaction, active tin-containing material and coating presoma, finally after reaction, obtain the composite material of the good stanniferous class activity substance content of lithium storage content and cycle performance.The content of reaction back stanniferous active material in composite material can be in the scope of 5%-60% (wt).
The feature that discharges and recharges of composite material possesses main body graphite and tin class material charge-discharge characteristic and composite attribute separately, also possesses the high lithium storage content characteristic of tin class material and the high stable circulation characteristic of graphite type material simultaneously.In the electrochemistry loop test composite material show tangible main body graphite and tin class material separately discharge and recharge feature, and composite attribute, this material can obtain to be better than the cyclical stability of tin class material, possesses the height ratio capacity characteristic of tin class material simultaneously again.
The present invention is described in further detail below by specific embodiment.
Embodiment 1
Preparation G-SnO
2-C (G is a graphite) composite negative pole material.
Take by weighing 32.4g urea and be dissolved in 85 ℃ the water, be configured to PH and be 10 solution for standby.Take by weighing spherical natural graphite 100g, 23.6gSnCl
4Be positioned over behind the stainless cylinder of steel airtight with 100g stainless steel pellet, be positioned on the planetary ball mill rotating speed ball milling with 200rpm after 60 minutes, slowly join in the urea liquid, in the process that adds, constantly stir, mixing speed is 300rpm, and reaction temperature is 85 ℃, and the reaction time is 4 hours, reaction end back filtration, washing, oven dry get G-Sn (OH)
4Composite material.
Take by weighing the 10g medium temperature coal pitch, be dissolved in the oxolane, be configured to 5% coating layer solution 400ml, standby.With above-mentioned G-Sn (OH)
4Composite material is immersed in the coating layer solution, stirs 1 hour with the rotating speed of 300rpm, makes G-Sn (OH)
4The composite material granular surface forms the coating film of one deck thin layer, dries oxolane then, continuous stirring-granulating in the process of oven dry.
Products therefrom is put into closed tube furnace,, rise to 400 ℃ with 5 ℃/minute heating rates with the logical high pure nitrogen of 15 liters/minute flows, be incubated 2 hours, rise to 1000 ℃ with 10 ℃/minute heating rate again, be incubated 2 hours, naturally be cooled to room temperature, promptly obtain G-SnO
2-C composite negative pole material.
With the above-mentioned G-SnO that makes
2-C composite negative pole material is anodal, and the lithium sheet is to electrode, and electrolyte is the LiPF of 1M
6EC/DMC (Vol 1: 1) solution, diaphragm paper is polyethylene, polypropylene composite diaphragm paper.Test charging and discharging currents density is 0.2mA/cm2, is 0V～1.5V by charging/discharging voltage.The G-SnO of preparation
2-C composite negative pole material initial charge capacity 590mAh/g, first charge-discharge capacity 490mAh/g, the coulombic efficiency that circulates first are that the attenuation rate of 83.1%, 20 average each circulation volume in circulation back is 0.5%.
Embodiment 2
Preparation G-Sn-Ag-C composite negative pole material.
Take by weighing 32.4gNaOH and be dissolved in 20 ℃ the water, be configured to PH and be 13 solution, standby; Take by weighing spherical natural graphite 100g, 70.8gSnCl
4, 91.8gAgNO
3(Sn: Ag=1: 2 mol ratios) and 100g stainless steel pellet be positioned over behind the stainless cylinder of steel airtight, be positioned on the planetary ball mill rotating speed ball milling with 600rpm after 30 minutes, slowly join in the NaOH solution, in the process that adds, constantly stir, mixing speed is 300rpm, and reaction temperature is 20 ℃, and the reaction time is 4 hours, reaction end back filtration, washing, oven dry get G-Sn (OH)
4-AgOH composite material.
Take by weighing the 30g medium temperature coal pitch, be dissolved in the pyridine, be configured to 5% coating layer solution 600ml, standby.Above-mentioned composite material is immersed in the coating layer solution, stirred 4 hours, make G-Sn (OH) with the rotating speed of 300rpm
4-AgOH composite material granular surface forms the coating film of one deck thin layer, dries pyridine then, continuous stirring-granulating in the process of oven dry.
Products therefrom is put into closed tube furnace; with the logical protectiveness mist of 15 liters/minute flows; V argon gas in the mist: V hydrogen=95: 5; and rise to 400 ℃ with 5 ℃/minute heating rate; be incubated 2 hours, rise to 1000 ℃ with 10 ℃/minute heating rate again, be incubated 2 hours; naturally be cooled to room temperature, promptly obtain the G-Sn-Ag-C composite negative pole material.
With the above-mentioned G-Sn-Ag-C composite negative pole material that makes is positive pole, and the lithium sheet is to electrode, and electrolyte is the LiPF of 1M
6EC/DMC (Vol 1: 1) solution, diaphragm paper is polyethylene, polypropylene composite diaphragm paper.Test charging and discharging currents density is 0.2mA/cm2, is 0V～1.5V by charging/discharging voltage.The G-Sn-Ag-C composite negative pole material initial charge capacity 463mAh/g of preparation, first charge-discharge capacity 398mAh/g, the coulombic efficiency that circulates first are that the attenuation rate of 85.9%, 20 average each circulation volume in circulation back is 0.5%.
Embodiment 3
Preparation G-Sn-Mg-C composite negative pole material.
Take by weighing 45.4gKOH and be dissolved in 50 ℃ the water, be configured to PH and be 13 solution, standby; Take by weighing spherical natural graphite 100g, 70.8gSnCl4,51.3gMgCl2 (Sn: Mg=1: 2 mol ratios) and 100g stainless steel pellet be positioned over behind the stainless cylinder of steel airtight, be positioned on the planetary ball mill rotating speed ball milling with 50rpm after 600 minutes, slowly join in the KOH solution, in the process that adds, constantly stir, mixing speed is 300rpm, and reaction temperature is 50 ℃, and the reaction time is 4 hours, reaction end back filtration, washing, oven dry get G-Sn (OH)
4-Mg (OH)
2Composite material.
Take by weighing the 10g medium temperature coal pitch, be dissolved in the acetone, be configured to 5% coating layer solution 200ml, standby.Above-mentioned composite material is immersed in the coating layer solution, stirred 4 hours, make G-Sn (OH) with the rotating speed of 300rpm
4-Mg (OH)
2The composite material granular surface forms the coating film of one deck thin layer, dries acetone then, continuous stirring-granulating in the process of oven dry.
Products therefrom is put into closed tube furnace; with logical protectiveness mist (the V helium: V hydrogen=80: 20) of 15 liters/minute flows; rise to 400 ℃ with 10 ℃/minute heating rates; be incubated 2 hours; rise to 1000 ℃ with 20 ℃/minute heating rate again; be incubated 2 hours, be cooled to room temperature naturally, promptly obtain the G-Sn-Mg-C composite negative pole material.
With the above-mentioned G-Sn-Mg-C composite negative pole material that makes is positive pole, and the lithium sheet is to electrode, and electrolyte is the LiPF of 1M
6EC/DMC (Vol 1: 1) solution, diaphragm paper is polyethylene, polypropylene composite diaphragm paper.Test charging and discharging currents density is 0.2mA/cm2, is 0V～1.5V by charging/discharging voltage.The G-Sn-Mg-C composite negative pole material initial charge capacity 467mAh/g of preparation, first charge-discharge capacity 394mAh/g, the coulombic efficiency that circulates first are that the attenuation rate of 84.3%, 20 average each circulation volume in circulation back is 0.6%.
Embodiment 4
Preparation G-Sn-Ni-C composite negative pole material.
Take by weighing the Ca (OH) of 34.8g
2Be dissolved in 60 ℃ the water, be configured to PH and be 8 solution, standby; Take by weighing spherical natural graphite 100g, 70.8gSnCl
4, 38.4gNi (NO
3)
2(Sn: Ni=4: 3 mol ratios) and 100g stainless steel pellet be positioned over behind the stainless cylinder of steel airtightly, be positioned on the planetary ball mill rotating speed ball milling with 100rpm after 400 minutes, slowly join Ca (OH)
2In the solution, constantly stirring in the process that adds, mixing speed is 300rpm, and reaction temperature is 60 ℃, and the reaction time is 4 hours, reacts the end back and filters, washs, dries, and gets G-Sn (OH)
4-Ni (OH)
2Composite material.
Take by weighing the 10g medium temperature coal pitch, be dissolved in the ethanol, be configured to 5% coating layer solution 200ml, standby.Above-mentioned composite material is immersed in the coating layer solution, stirred 4 hours, make G-Sn (OH) with the rotating speed of 300rpm
4-Ni (OH)
2The composite material granular surface forms the coating film of one deck thin layer, dries ethanol then, continuous stirring-granulating in the process of oven dry.
Products therefrom is put into closed tube furnace; with logical protectiveness mist (the V neon: V hydrogen=90: 10) of 15 liters/minute flows; rise to 400 ℃ with 10 ℃/minute heating rates; be incubated 2 hours; rise to 1000 ℃ with 20 ℃/minute heating rate again; be incubated 2 hours, be cooled to room temperature naturally, promptly obtain the G-Sn-Ni-C composite negative pole material.
With the above-mentioned G-Sn-Ni-C composite negative pole material that makes is positive pole, and the lithium sheet is to electrode, and electrolyte is the LiPF of 1M
6EC/DMC (Vol 1: 1) solution, diaphragm paper is polyethylene, polypropylene composite diaphragm paper.Test charging and discharging currents density is 0.2mA/cm2, is 0V～1.5V by charging/discharging voltage.The G-Sn-Ni-C composite negative pole material initial charge capacity 560mAh/g of preparation, first charge-discharge capacity 469mAh/g, the coulombic efficiency that circulates first are that the attenuation rate of 83.7%, 20 average each circulation volume in circulation back is 0.6%.
Embodiment 5
Preparation G-Sn-Cu-C composite negative pole material.
Take by weighing 48.6g urea and be dissolved in 70 ℃ the water, be configured to PH and be 10 solution, standby; Take by weighing spherical natural graphite 100g, 70.8gSnCl
4, 36.3gCuCl
2(Sn: Cu=1: 1 mol ratio) and 100g stainless steel pellet be positioned over behind the stainless cylinder of steel airtight, be positioned on the planetary ball mill rotating speed ball milling with 100rpm after 400 minutes, slowly join in the urea liquid, in the process that adds, constantly stir, mixing speed is 300rpm, and reaction temperature is 70 ℃, and the reaction time is 4 hours, reaction end back filtration, washing, oven dry get G-Sn (OH)
4-Cu (OH)
2Composite material.
Take by weighing the 10g medium temperature coal pitch, be dissolved in the ethanol, be configured to 5% coating layer solution 200ml, standby. above-mentioned composite material is immersed in the coating layer solution, stirred 4 hours, make G-Sn (OH) with the rotating speed of 300rpm
4-Cu (OH)
2The composite material granular surface forms the coating film of one deck thin layer, dries ethanol then, continuous stirring-granulating in the process of oven dry.
Products therefrom is put into closed tube furnace; with logical protectiveness mist (the V helium: V carbon monoxide=85: 15) of 15 liters/minute flows; rise to 400 ℃ with 10 ℃/minute heating rates; be incubated 2 hours; rise to 1000 ℃ with 20 ℃/minute heating rate again; be incubated 2 hours, be cooled to room temperature naturally, promptly obtain the G-Sn-Cu-C composite negative pole material.
With the above-mentioned G-Sn-Cu-C composite negative pole material that makes is positive pole, and the lithium sheet is to electrode, and electrolyte is the LiPF of 1M
6EC/DMC (Vol 1: 1) solution, diaphragm paper is polyethylene, polypropylene composite diaphragm paper.Test charging and discharging currents density is 0.2mA/cm2, is 0V～1.5V by charging/discharging voltage.The G-Sn-Cu-C composite negative pole material initial charge capacity 515mAh/g of preparation, first charge-discharge capacity 452mAh/g, the coulombic efficiency that circulates first are that the attenuation rate of 87.8%, 20 average each circulation volume in circulation back is 0.6%.
Claims (14)
1. tin carbon compound electrode material for lithium ion battery cathode, it is characterized in that: described combination electrode material comprises graphite body, coats carbon-coating and stanniferous class lithium storage materials, described stanniferous class lithium storage materials circle in graphite surface and coat between the carbon-coating or the boundary in the interlayer of graphite or coat the interlayer of carbon-coating, described combination electrode material prepares by the following method:
(1) graphite material is carried out ball milling with mixing up pink salt;
(2) react in the mixture adding aqueous slkali that step (1) is obtained, afterwards filtering drying;
(3) organic solution of preparation carbon coated layer material, and add the product that step (2) obtains therein, react back oven dry granulation;
(4) the granulated high temperature solid state reaction that carries out that step (3) is obtained.
2. a kind of tin carbon compound electrode material for lithium ion battery cathode according to claim 1 is characterized in that: described stanniferous class lithium storage materials comprises the compound of tin or tin.
3. a kind of tin carbon compound electrode material for lithium ion battery cathode according to claim 2 is characterized in that: the compound of described tin comprises the oxide of tin or the alloy of tin, and the oxide of described tin comprises SnO
2, the alloy of described tin comprises Sn-Ag alloy, Sn-Mg alloy, Sn-Ni alloy or Sn-Cu alloy.
4. according to the arbitrary described a kind of tin carbon compound electrode material for lithium ion battery cathode of claim 1～3, it is characterized in that: the content of described stanniferous class lithium storage materials in combination electrode material is 5%～60%wt.
5. the preparation method of a tin carbon compound electrode material for lithium ion battery cathode, described combination electrode material comprises graphite body, coats carbon-coating and stanniferous class lithium storage materials, described stanniferous class lithium storage materials circle in graphite surface and coat between the carbon-coating or the boundary in the interlayer of graphite or coat the interlayer of carbon-coating, described method comprises step:
(1) graphite material is carried out ball milling with mixing up pink salt;
(2) react in the mixture adding aqueous slkali that step (1) is obtained, afterwards filtering drying;
(3) organic solution of preparation carbon coated layer material, and add the product that step (2) obtains therein, react back oven dry granulation;
(4) the granulated high temperature solid state reaction that carries out that step (3) is obtained.
6. preparation method according to claim 5 is characterized in that: described method further comprises step (5) afterwards in step (4): reduce to room temperature naturally after high temperature solid state reaction finishes and obtain tin carbon compound electrode material.
7. according to claim 5 or 6 described preparation methods, it is characterized in that: described graphite material comprises natural flake graphite, spherical natural graphite or Delanium, describedly mixes up the mixture that pink salt comprises pink salt or pink salt and other slaines.
8. preparation method according to claim 7 is characterized in that: described pink salt is SnCl
4, described other slaines comprise AgNO
3, MgCl
2, Ni (NO
3)
2Or CuCl
2
9. according to claim 5 or 6 described preparation methods, it is characterized in that: described step (1) specifically is meant, with graphite material with mixing up pink salt and pellet places hermetically sealed can, and on planetary ball mill, carry out ball milling, the weight ratio of described pellet and graphite material is 0.5: 1～10: 1, the rotating speed of described ball milling is 20r/min～600r/min, and the time of described ball milling is 0.5 hour～100 hours.
10. according to claim 5 or 6 described preparation methods, it is characterized in that: described step (2) specifically is meant, slowly add the mixture behind the ball milling in the aqueous slkali, constantly stir when adding, and at 20 ℃～100 ℃ following reaction filtering dryings after 0.5～100 hour, the pH value of described aqueous slkali is 7.5～13.
11. according to claim 5 or 6 described preparation methods, it is characterized in that: described step (3) specifically is meant, compound concentration is the organic solution of the carbon coated layer material of 3%～7%wt, under continuous condition of stirring, add the product that step (2) obtains, reacted 0.5～100 hour, constantly stir in the course of reaction, dry out solvent afterwards, continuous stirring-granulating in drying course.
12. preparation method according to claim 11 is characterized in that: the solvent of the organic solution of described carbon coated layer material is one or more in pyridine, acetone, oxolane, the ethanol, and described carbon coated layer material is a medium temperature coal pitch.
13. according to claim 5 or 6 described preparation methods; it is characterized in that: described step (4) specifically is meant; the granulated good reaction vessel of air-tightness that places that step (3) is obtained; under protective atmosphere, heat up in 400～1600 ℃ and carry out high temperature solid state reaction, and be incubated 10～240 minutes with the heating rate of 2～30 ℃/min.
14. preparation method according to claim 13; it is characterized in that: described step (4) specifically is meant; the granulated good reaction vessel of air-tightness that places that step (3) is obtained; heating rate with 3～15 ℃/min under protective atmosphere heats up in 400～600 ℃; and be incubated 10～240 minutes; heat up in 800～1600 ℃ with the heating rate of 7～30 ℃/min more afterwards; and be incubated 10～240 minutes; described protective atmosphere comprises protective gas and reducibility gas, and the volume content of described reducibility gas is 0～20%.
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|---|---|---|---|
| CN200610020272A CN101017893B (en) | 2006-02-08 | 2006-02-08 | A tin carbon compound electrode material for lithium ion battery cathode and preparing method |
| HK07114101.0A HK1105717A1 (en) | 2006-02-08 | 2007-12-26 | A tin-carbon electrode composite used in cathode of li-ion battery and its producing method |
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|---|---|---|---|
| CN200610020272A CN101017893B (en) | 2006-02-08 | 2006-02-08 | A tin carbon compound electrode material for lithium ion battery cathode and preparing method |
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| CN101017893B true CN101017893B (en) | 2010-05-12 |
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| CN101388447B (en) * | 2007-09-14 | 2011-08-24 | 清华大学 | Negative pole for lithium ionic cell and preparing method thereof |
| CN101997110B (en) * | 2009-08-19 | 2012-11-28 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing stannum-carbon composite cathode material for lithium ion battery by utilizing thermal carbon reduction method |
| CN102054970B (en) * | 2009-11-02 | 2013-02-13 | 五邑大学 | Method for preparing tin-carbon cathode material of lithium ion battery |
| CN101969113B (en) * | 2010-09-21 | 2012-11-07 | 上海大学 | Preparation method of graphene-base tin dioxide composite anode material for lithium ion batteries |
| CN102340001A (en) * | 2011-08-26 | 2012-02-01 | 奇瑞汽车股份有限公司 | Method for preparing high-specific-capacity silicon carbon and tin carbon composite anode material |
| CN103137951B (en) * | 2011-11-22 | 2016-08-31 | 宁波杉杉新材料科技有限公司 | A kind of tin-based composite anode materials for lithium-ion batteries and preparation method thereof |
| GB2508218A (en) * | 2012-11-26 | 2014-05-28 | Leclanch S A | Electrode for the reduction of gassing in lithium titanate cells |
| CN103050671A (en) * | 2012-11-30 | 2013-04-17 | 东莞市翔丰华电池材料有限公司 | Preparation method of tin carbon composition material for lithium ion battery negative pole |
| CN104409728B (en) * | 2014-05-31 | 2017-02-08 | 福州大学 | Method for preparing tin-carbon anode/lithium iron phosphate cathode lithium ion battery based on 3D printing technology |
| CN104103808B (en) * | 2014-07-31 | 2016-07-27 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery lamellar stannum carbon composite and preparation method thereof |
| CN104766962B (en) * | 2015-04-17 | 2017-12-05 | 辽宁工程技术大学 | The charcoal bag of sodium-ion battery covers the preparation method of graphite oxide/Sn composite negative pole materials |
| CN104993108A (en) * | 2015-05-29 | 2015-10-21 | 田东 | Preparation method of lithium titanate/tin composite cathode material |
| CN105140496A (en) * | 2015-08-07 | 2015-12-09 | 田东 | Preparation method for high-capacity and high-magnification negative electrode material |
| CN105140483A (en) * | 2015-08-07 | 2015-12-09 | 田东 | Preparation method of modified lithium battery anode material |
| CN105140480A (en) * | 2015-08-07 | 2015-12-09 | 田东 | Preparation method of high-capacity tin-carbon anode material |
| CN105161671A (en) * | 2015-08-07 | 2015-12-16 | 田东 | Preparation method for tin-carbon composite negative material |
| CN105140481A (en) * | 2015-08-07 | 2015-12-09 | 田东 | Preparation method of high-capacity lithium-ion battery anode material |
| CN105990572A (en) * | 2016-04-27 | 2016-10-05 | 厦门百美特生物材料科技有限公司 | Tin-carbon composite material as well as preparation method and application thereof |
| CN105958026B (en) * | 2016-06-18 | 2018-10-02 | 湖南中科星城石墨有限公司 | A kind of preparation method of negative electrode of lithium ion battery graphite tin composite material |
| CN107895785A (en) * | 2017-11-14 | 2018-04-10 | 复旦大学 | A kind of compound anode material of lithium-ion battery and preparation method thereof |
| CN108565411A (en) * | 2018-03-20 | 2018-09-21 | 无锡新锂辰能源科技有限公司 | A kind of Sn-C composite electrodes material and its preparation method and application |
| CN108807873B (en) * | 2018-04-25 | 2021-06-25 | 深圳市翔丰华科技股份有限公司 | Method for preparing copper-antimony doped tin-carbon lithium ion negative electrode material |
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