CN102427127A - Stannum oxide/stannum-carbon composite material, and preparation method and application thereof - Google Patents

Stannum oxide/stannum-carbon composite material, and preparation method and application thereof Download PDF

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Publication number
CN102427127A
CN102427127A CN2011103963708A CN201110396370A CN102427127A CN 102427127 A CN102427127 A CN 102427127A CN 2011103963708 A CN2011103963708 A CN 2011103963708A CN 201110396370 A CN201110396370 A CN 201110396370A CN 102427127 A CN102427127 A CN 102427127A
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tin
oxide
preparation
composite material
ball
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朱敏
刘辉
胡仁宗
刘江文
曾美琴
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a stannum oxide/stannum-carbon composite material, and a preparation method and application thereof. The preparation method comprises the following steps of: mixing stannum powder and carbon powder according to the mass ratio of 1:0.3 to 1:0.7, performing vacuumizing, charging oxygen, and performing ball-milling by adopting a dielectric barrier discharge plasma-aided high-energy ball-milling method to obtain the stannum oxide/stannum-carbon composite material which is a Sn and SnOx/C composite material, wherein oxygen pressure in a ball milling process is ensured to be 0.1 to 0.12MPa. The structure of the composite material is that: amorphous-nanocrystalline stannum oxide is coated on the surface of stannum to form a core shell structure, and the core shell structure is uniformly distributed in a graphite substrate. When used as an anode material for a lithium ion battery, the Sn and SnOx/C composite material has high capacity and high cycle performance. The preparation method is simple, high in powder yield and pollution-free.

Description

Tin-oxide/tin carbon composite
Technical field
The present invention relates to lithium ion battery negative material, be specifically related to tin-oxide/tin carbon composite.
Technical background
Lithium ion battery has great strategic importance at new energy field, is the hot spot technology of current generation.The selection of negative material system and performance thereof are one of key factors of decision lithium ion battery performance of new generation.The capacity of the carbon negative pole material of Traditional businessization reaches capacity, and the problem of its essence is the low (372mAhg of the theoretical capacity of material with carbon element -1).In numerous non-carbon negative pole material systems after deliberation, the metal Sn system of high power capacity is realize using among a small circle and the lithium ion battery negative material of sustainable exploitation, is the research focus of novel negative material in recent years.In addition, the oxide of tin also is the lithium ion battery negative material of high-quality, SnO and SnO 2Theoretical capacity be respectively 875mAhg -1And 782mAhg -1, can satisfy the requirement of lithium ion battery instantly to the high-energy-density development.But research shows, single metal Sn or the oxide of Sn are during as the negative material of lithium ion battery, because the huge volumetric expansion of Sn causes electrode failure and can't obtain excellent cycle performance.
Addressing the above problem the most frequently used and effective way is to adopt composite material.With the compound excellent cycle performance of material with carbon element and the characteristics of tin-based material high power capacity of having combined of carbon and tin-based material, be one of method of using always.
Summary of the invention
Unresolved the problems referred to above the object of the present invention is to provide that a kind of technology is simple, excellent performance, the tin-oxide/tin carbon composite that can produce in batches.
Tin-oxide/tin the carbon composite of the present invention's preparation (also is SnSnO x/ C composite material), be composited by tin, graphite and amorphous-nano-crystalline oxide, wherein, the top layer that the amorphous-nano-crystalline tin-oxide is coated on tin forms nucleocapsid structure, and said nucleocapsid structure is evenly distributed in the graphite matrix.
The preparation method of said tin-oxide/tin carbon composite; Its step is following: with glass putty and carbon dust according to mass ratio 1: 0.3-1: after 0.7 the mixed; Extracting vacuum also charges into oxygen; Carry out ball milling then, obtain tin-oxide/tin carbon composite, guarantee that oxygen pneumatic is 0.1-0.12Mpa in the mechanical milling process.
Further, said ball milling adopts dielectric barrier discharge plasma auxiliary high-energy ball-milling method, adopts discharge gas medium oxygen in the mechanical milling process.
The ball powder ratio of mill ball quality and glass putty and carbon dust gross mass is 30 during ball milling: 1-50: 1, and the ball milling time is 2.5~25h.
Tin-oxide provided by the present invention/tin carbon composite is as the application of lithium ion battery negative material.
Compared with prior art, the present invention has following advantage:
(1) SnSnO of the present invention xThe preparation method of/C composite material is simple.Adopt the Prepared by Ball Milling tin-oxide first, adopt chemical reduction method to prepare tin oxide usually with existing research and compare, powder outlet quantity is big, and efficient is high, and process is simple, needs the parameter of control few, and environmentally safe.
(2) SnSnO provided by the present invention x/ C composite material than the Metal Substrate negative material of prepared by other, has been taken into account high power capacity and high cyclical stability characteristics as lithium ion battery negative material.
Description of drawings
Fig. 1 is the prepared SnSnO of embodiment 4 xThe XRD spectra of/C composite material;
Fig. 2 is the prepared SnSnO of embodiment 4 xThe SEM figure of/C composite material;
Fig. 3 is the prepared SnSnO of embodiment 4 xThe HTEM figure of/C composite material;
Fig. 4 is the prepared SnSnO of embodiment 8 xCharging and discharging curve figure under the difference circulation of/C composite material;
Fig. 5 is embodiment 4 and the prepared SnSnO of embodiment 8 xThe cycle performance curve comparison diagram of/C composite material.
Embodiment
Below in conjunction with embodiment, the present invention is done to specify further, but execution mode of the present invention is not limited thereto.
The dielectric barrier discharge plasma auxiliary high-energy ball grinding method of introducing among the patent ZL200510036231.9 is adopted in the preparation of various embodiments of the present invention composite material.
The concrete steps of dielectric barrier discharge plasma auxiliary high-energy ball grinding method are:
(1) install the front shroud and the electrode bar of ball grinder, and link to each other front shroud with the positive and negative two-stage of plasma electrical source respectively with iron core in the electrode bar, wherein, the interior iron core of electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(2) the good starting powder of abrading-ball and proportioning of in ball grinder, packing into;
(3) through vacuum valve ball grinder is vacuumized, charge into discharge gas medium O then 2, make the force value in the ball grinder reach 0.1-0.12Mpa;
(4) connect plasma electrical source, it is 15KV that plasma electrical source voltage is set, and electric current is 1.5A; Discharge frequency 60KHz; Start drive motors and drive the exciting piece, make frame and the ball grinder that is fixed on the frame vibrates simultaneously, carry out dielectric barrier discharge plasma auxiliary high-energy ball milling.Said exciting piece adopts double-amplitude 5mm~10mm, motor speed 930~1400r/min.
With the SnSnO behind the ball milling x/ C composite material conductive agent super-p and binding agent Pvdf mix to be coated on by mass ratio and are made into electrode slice on the Copper Foil at 8: 1: 1.In the argon gas atmosphere glove box, with lithium metal as to electrode, ethylene carbonate (EC)+dimethyl carbonate (DMC)+1MLiPF 6Be electrolyte, be assembled into button cell and test.Test condition is: charging and discharging currents density is 0.4mAhcm -2, discharging and recharging by voltage is 0.01V~1.2V (vs.Li +/ Li).
Embodiment 1
After tin raw material, graphite raw material powder, wherein the mass ratio of graphite raw material and tin raw material is 0.3: 1.Obtain the tin-oxide/tin carbon composite behind the ball milling according to above-mentioned ball grinding method, said discharge gas medium is an oxygen, and vacuum degree is 0.1Mpa, and the ball powder mass ratio of abrading-ball and tin carbon mixed-powder is 50: 1, and the ball milling time is 2.5h; Carry out charge-discharge test according to above-mentioned battery testing condition and step then, the SnSnO that obtains preparing x/ C composite material its first discharge capacity be 627mAhg -1
Embodiment 2
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 1 are basic identical, and different is that raw material carries out proportioning according to Sn: C=1: X, and wherein the value of X is X=0.5, and the ball milling time is 5h.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.The SnSnO of preparation x/ C composite material its first discharge capacity be 583mAhg -12, capacity remains on 320mAhg after 40 circulations -1
Embodiment 3
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 1 are basic identical, and different is is 7.5h the ball milling time.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.The preparation the SnSnOx/C composite material its first discharge capacity be 575.1mAhg -1, 100 times circulation back capacity remains on 240mAhg -1
Embodiment 4
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 1 are basic identical, and different is is 10h the ball milling time.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.SnSnOx/C composite material to prepared carries out the XRD figure analysis of spectrum, and its component is amorphous-nano-crystalline tin-oxide, tin and graphite (Fig. 1); Wherein, the top layer that tin-oxide is coated on tin forms nucleocapsid structure, and nucleocapsid structure is evenly distributed in (Fig. 2 and Fig. 3) in the graphite matrix; Because this structure can alleviate the change in volume of tin in charge and discharge process effectively, thus use as lithium cell cathode material with it, its first discharge capacity be 1001mAhg -1, 100 times circulation back capacity remains on 400mAhg -1(Fig. 4).
Embodiment 5
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 1 are basic identical, and different is is 20h the ball milling time.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.The SnSnO of preparation x/ C composite material its first discharge capacity be 723mAhg -1, 100 times circulation back capacity remains on 200mAhg -1
Embodiment 6
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 5 are basic identical, and different is is 25h the ball milling time.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.The SnSnO of preparation x/ C composite material has excellent capability retention (Fig. 5), its first reversible capacity be 1345mAhg -1, 100 times circulation back capacity remains on 500mAhg -1
Embodiment 7
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 1 are basic identical, and different is that raw material carries out proportioning according to Sn: C=1: X, and wherein the value of X is X=0.7, and the ball milling time is 5h.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.The SnSnO of preparation x/ C composite material its first reversible capacity be 520mAhg -1
Embodiment 8
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 1 are basic identical, and different is that raw material carries out proportioning according to Sn: C=1: X, and wherein the value of X is X=0.7, and the ball milling time is 10h.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.The SnSnO of preparation x/ C composite material its first reversible capacity be 490mAhg -1, 100 times circulation back capacity remains on 300mAhg -1
Embodiment 9
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 1 are basic identical, and different is that raw material carries out proportioning according to Sn: C=1: X, and wherein the value of X is X=0.3, and the ball milling time is 5h.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.The SnSnO of preparation x/ C composite material its first reversible capacity be 625mAhg -1
Embodiment 10
Adopt the method for the auxiliary ball milling of dielectric barrier discharge plasma to prepare SnSnO x/ C composite material, its step and embodiment 1 are basic identical, and different is that raw material carries out proportioning according to Sn: C=1: X, and wherein the value of X is X=0.3, and the ball milling time is 10h.Carry out charge-discharge test after above-mentioned powder processed lithium ion battery negative electrode slice and assembled battery.The SnSnO of preparation x/ C composite material its first reversible capacity be 584mAhg -1, 100 times circulation back capacity is 200mAhg -1
As stated, can realize preferably that just the present invention, the foregoing description are merely part embodiment of the present invention, be not to be used for limiting practical range of the present invention; Be that all equalizations of doing according to content of the present invention change and modification, all contained by claim of the present invention scope required for protection.

Claims (7)

1. tin-oxide/tin carbon composite; It is characterized in that being composited by tin, graphite and amorphous-nano-crystalline tin-oxide; The top layer that said amorphous-nano-crystalline tin-oxide is coated on tin forms nucleocapsid structure, and this nucleocapsid structure is evenly distributed in the graphite matrix.
2. the preparation method of the said tin-oxide of claim 1/tin carbon composite; It is characterized in that step is following: with glass putty and carbon dust according to mass ratio 1: 0.3-1: after 0.7 the mixed; Extracting vacuum also charges into oxygen; Carry out ball milling then, obtain tin-oxide/tin carbon composite, oxygen pneumatic is 0.1-0.12Mpa in the mechanical milling process.
3. preparation method according to claim 2 is characterized in that said ball milling adopts dielectric barrier discharge plasma auxiliary high-energy ball-milling method.
4. preparation method according to claim 3 is characterized in that said dielectric barrier discharge plasma auxiliary high-energy ball-milling method adopts discharge gas medium oxygen.
5. preparation method according to claim 3, the quality of abrading-ball and the ball powder ratio of glass putty and carbon dust gross mass are 30 when it is characterized in that said ball milling: 1-50: 1.
6. preparation method according to claim 3 is characterized in that the said ball milling time is 2.5~25h.
7. the said tin-oxide of claim 1/tin carbon composite is as the application of lithium ion battery negative material.
CN2011103963708A 2011-12-02 2011-12-02 Stannum oxide/stannum-carbon composite material, and preparation method and application thereof Pending CN102427127A (en)

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CN103236528A (en) * 2013-04-22 2013-08-07 华南理工大学 Germanium-carbon-graphene composite material, and preparation method and application thereof
CN103247803A (en) * 2013-04-16 2013-08-14 华南理工大学 Graphene-cladding nano germanium composite material as well as preparation method and application thereof
CN106410166A (en) * 2016-11-30 2017-02-15 华南理工大学 Tin oxide/tin/few-layer graphene composite material as well as preparation method and application thereof
CN108365207A (en) * 2018-03-27 2018-08-03 北京化工大学 A kind of negative electrode of lithium ion battery stannous oxide/carbon composite and its synthetic method
WO2018209912A1 (en) * 2017-05-17 2018-11-22 华南理工大学 Tin sulfide/sulfur/few-layer graphene composite material, preparation method therefor and application thereof
CN113355687A (en) * 2021-04-20 2021-09-07 广东石油化工学院 Tin-based bimetallic carbide @ carbon nanochain core-shell structure and preparation method and application thereof

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CN103247803A (en) * 2013-04-16 2013-08-14 华南理工大学 Graphene-cladding nano germanium composite material as well as preparation method and application thereof
CN103236528A (en) * 2013-04-22 2013-08-07 华南理工大学 Germanium-carbon-graphene composite material, and preparation method and application thereof
CN103236528B (en) * 2013-04-22 2016-01-20 华南理工大学 A kind of germanium carbon graphite alkene composite material and its preparation method and application
CN106410166A (en) * 2016-11-30 2017-02-15 华南理工大学 Tin oxide/tin/few-layer graphene composite material as well as preparation method and application thereof
WO2018209912A1 (en) * 2017-05-17 2018-11-22 华南理工大学 Tin sulfide/sulfur/few-layer graphene composite material, preparation method therefor and application thereof
CN108365207A (en) * 2018-03-27 2018-08-03 北京化工大学 A kind of negative electrode of lithium ion battery stannous oxide/carbon composite and its synthetic method
CN108365207B (en) * 2018-03-27 2021-01-19 北京化工大学 Lithium ion battery cathode stannous oxide/carbon composite material and synthesis method thereof
CN113355687A (en) * 2021-04-20 2021-09-07 广东石油化工学院 Tin-based bimetallic carbide @ carbon nanochain core-shell structure and preparation method and application thereof

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Application publication date: 20120425