CN105118966A - Sn-C composite material with high N content of lithium battery cathode and preparation method of Sn-C composite material - Google Patents

Sn-C composite material with high N content of lithium battery cathode and preparation method of Sn-C composite material Download PDF

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CN105118966A
CN105118966A CN201510600582.1A CN201510600582A CN105118966A CN 105118966 A CN105118966 A CN 105118966A CN 201510600582 A CN201510600582 A CN 201510600582A CN 105118966 A CN105118966 A CN 105118966A
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lithium battery
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CN105118966B (en
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李忠涛
邓深圳
王书敬
王元坤
吴明铂
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China University of Petroleum East China
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract

The invention relates to a composite material of a lithium battery cathode. The composite material is prepared according to a method taking DAMN as a modifier during N doping of graphite oxide. SnCl4.5H2O is added in the N doping process, and a composite structure of carbon nitride and tin oxide is formed through high-temperature carbonization. The invention further provides a SnO2/CxNy/GN composite material which is controllably prepared according to a one-step hydro thermal method and high in N content. The SnO2/CxNy/GN composite material is high in electrochemical property while being used for preparing the lithium battery cathode; due to nano-dispersion of SnO2 particles, cross-linking polymerization between the surfaces of the SnO2 particles and N-doped graphene, and introduction of DAMN, not only is the conductibility of graphite oxide improved, but also more reaction active sites are provided for reaction with SnO2 nanocrystalline, and the SnO2 nano-particles are stably and uniformly dispersed in a lamella of carbon nitride and graphene.

Description

A kind of high nitrogen-containing tin carbon composite for cathode of lithium battery and preparation method
Technical field
The present invention relates to the preparation of composite material, particularly a kind of composite material for cathode of lithium battery.
Background technology
The advantages such as monomer voltage is high owing to having for lithium ion battery, energy density is large, have extended cycle life, safety and environmental protection, and be widely used in various electronic product.The performance of lithium ion battery depends primarily on the performance of positive and negative electrode material.Therefore, the raising of performance of lithium ion battery depends primarily on the raising of positive and negative electrode material property.
The negative material of current business-like lithium ion battery is graphite-based negative material.But graphite-based negative material capacity is low, voltage delay, can not meet the demand of people.And transition metal oxide has higher theoretical specific capacity, but it easily expands at charge and discharge process volume, causes cyclical stability poor.In order to overcome these shortcomings, people concentrate on the lithium ion battery negative material studied and have compared with height ratio capacity and cyclical stability simultaneously.In these researchs, SnO 2high theoretical capacity (782mAhg in cyclic process -1), attract a lot of concern.Carbon coated tin oxide negative material simultaneously in conjunction with the respective advantage of carbon and tin, can show excellent performance.But current carbon encapsulated material, the nanoparticle relatively uneven due to it and the low electric conductivity of carbon coated, make its capacity hold facility still limited.And before some prepare the method relative complex of carbon encapsulated material.Therefore find simply a kind of and SnO can be ensured simultaneously 2the method of the structure of the carbon base body of the dispersed and conduction of nanoparticle, has great importance.
Find to there is the material with carbon element that hetero-atom (as boron, nitrogen, sulphur, phosphorus etc.) adulterates and than unadulterated material with carbon element, there is higher specific capacity and better cyclical stability according to research before.And in these hetero-atoms, because the electronegativity of nitrogen is larger than carbon, atomic radius is less than carbon, doping nitrogen-atoms will fill up the defective bit in graphite oxide conjugated system, the oxygen-containing functional group in graphene sheet layer is converted to the higher C=N key of conjugation regularity simultaneously.Some amino-compounds contain active higher group, while raising graphite oxide conductivity, also for the compound of graphene oxide and inorganic material provides more reaction active site.Therefore, nitrogen-doped carbon material is very promising lithium ion battery electrode material.
Summary of the invention
For the defect existed in prior art, the object of this invention is to provide a kind of composite material for cathode of lithium battery and preparation method thereof.
The present invention is achieved through the following technical solutions:
For a composite material for cathode of lithium battery, adopt and be prepared from by cyano-containing and amino organic substance, pink salt and graphite oxide three kinds of raw materials.
On the basis of such scheme, described cyano-containing and amino organic substance are diaminomaleonitrile.
On the basis of such scheme, described pink salt is SnCl45H2O.
On the basis of such scheme, graphite oxide is ultrasonic disperse in distilled water, obtains graphene oxide solution.
On the basis of such scheme, the concentration of described graphite oxide solution alkene is 0.3-3.0mgmL -1.
On the basis of such scheme, graphene oxide solution adds diaminomaleonitrile under being heated to the condition of 30-60 DEG C.
On the basis of such scheme, after diaminomaleonitrile dissolves completely, add SnCl 45H 2o.
On the basis of such scheme, SnCl 45H 2o dissolves rear mixed liquor completely and react 8-20h under 120-180 DEG C of condition.
On the basis of such scheme, described reaction is carried out in water heating kettle.
On the basis of such scheme, product calcines more than 2h at 400-600 DEG C after centrifuge washing drying.
On the basis of such scheme, calcining carries out under atmosphere of inert gases.
The invention has the beneficial effects as follows:
The present invention adopts the SnO of one step hydro thermal method controlled synthesis high nitrogen content 2/ C xn y/ GN composite material, shows good chemical property when this composite material is used for lithium ion battery negative.SnO 2the nano-scale dispersion of particle and the cross-linked polymeric of surface and nitrogen-doped graphene thereof.The introducing of diaminomaleonitrile not only increases the conductivity of graphite oxide, provides more reaction active site and SnO simultaneously 2nanocrystalline reaction, makes SnO 2being dispersed in carbonitride and graphene sheet layer of nanoparticles stable.
Accompanying drawing explanation
The present invention has following accompanying drawing:
Fig. 1 is SnO 2/ C xn y, SnO 2/ DAMN/GO and SnO 2/ C xn ythe XRD collection of illustrative plates of/GN, wherein (a) SnO 2/ C xn yxRD scheme (b) SnO 2the XRD of/DAMN/GO schemes (c) SnO 2/ C xn ythe XRD figure of/GN;
Fig. 2 is SnO 2/ C xn y, SnO 2/ DAMN/GO and SnO 2/ C xn ythe TEM figure and SnO of/GN 2/ C xn ythe HR-TEM figure of/GN, wherein (a) SnO 2/ C xn ytEM scheme (b) SnO 2the TEM of/DAMN/GO schemes (c) SnO 2/ C xn ythe TEM of/GN schemes (d) SnO 2/ C xn ythe HR-TEM figure of/GN;
Fig. 3 is SnO 2/ C xn y, SnO 2/ DAMN/GO and SnO 2/ C xn ythe FT-IR collection of illustrative plates of/GN, wherein (a) SnO 2/ C xn yfTIR scheme (b) SnO 2the FTIR of/DAMN/GO schemes (c) SnO 2/ C xn ythe FTIR figure of/GN;
Fig. 4 is SnO 2/ C xn ythe aerial TGA figure of/GN;
Fig. 5 is SnO 2/ C xn y, SnO 2/ DAMN/GO and SnO 2/ C xn y/ GN is at 100mAg -1current density under stable circulation performance and SnO 2/ C xn ythe coulombic efficiency figure of/GN;
Fig. 6 is SnO 2/ C xn y, SnO 2/ DAMN/GO and SnO 2/ C xn ythe AC impedance figure of/GN;
Fig. 7 is SnO 2/ C xn ythe high rate performance figure of/GN material;
Fig. 8 is SnO 2/ C xn ythe cyclic voltammetric of/GN and capacity voltage pattern;
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
First the Hummers method synthesis graphite oxide utilizing graphite powder to pass through to optimize.By 200mg graphite oxide ultrasonic disperse 2 hours in 200ml distilled water, form graphene oxide solution, the solution liquid obtained is labeled as solution A.Solution A is heated to 45 DEG C, slowly adds 0.80g diaminomaleonitrile under stirring, make it fully dissolve, the solution obtained is designated as solution B.Under stirring, by 1.20gSnCl 45H 2o is dissolved in above-mentioned solution B.Then, mixed liquor is transferred to water heating kettle, hydro-thermal 12 hours at 150 DEG C.After reaction, be naturally down to room temperature.By products therefrom centrifuge washing for several times, product is dry at 70 DEG C.Finally, at high purity N 2calcine 2 hours for 500 DEG C in tube furnace under atmosphere, can SnO be obtained 2/ C xn y/ GN composite material.By above-mentioned identical method, prepare the composite material not adding graphite oxide and non-carbonization treatment respectively, be labeled as SnO respectively 2/ C xn yand SnO 2/ DAMN/GO.
Analysis and characterization
Dutch X ' PertPROMPD type X-ray diffractometer (XRD, CuK α, λ=0.15406nm) is adopted to carry out structure, material phase analysis to sample.German STA409PCLuxx thermogravimetric analyzer (TGA) is adopted to test the tin ash content of sample in air atmosphere.By observing pattern and the structure of sample with Japanese HitachiS-4800 type scanning electron microscopy (SEM) and JEM-2100UHR type transmission electron microscope (TEM).In sample, contained element and functional group are analyzed by U.S. ThermoNicoletNEXUS670 type examination of infrared spectrum instrument (FT-IR).
Result and analysis:
There is the diffraction maximum that five wider in Fig. 1 (a), (b), (c), belong to SnO respectively 2(110), (101), (200), (211) and (301) crystal face diffraction (JCPDSNo.41-1445).Wide in range diffraction maximum shows SnO in prepared composite material 2all remain on less size.Can also find from figure, (c), compared with (a), after adding Graphene, the peak width of diffraction maximum becomes large, and what Graphene was described adds the dispersion facilitating granules of stannic oxide.C (), compared with (b), after high-temperature heat treatment, the peak width of diffraction maximum diminishes, illustrate that high-temperature heat treatment makes granules of stannic oxide reunite.
For verifying the microstructure of composite material further, transmissioning electric mirror test (shown in Fig. 2) is done to three kinds of composite materials.In Fig. 2, (c) compares with (b) figure, and tin oxide particle diameter becomes large, and illustrate after high temperature cabonization, slight reunion occurs tin oxide grain.C () is compared with (a) figure, the dispersiveness adding Graphene rear oxidation tin particles obtains obvious improvement, and the dispersion adding energy accelerating oxidation tin of Graphene is described.This and the characterization result of XRD collection of illustrative plates are consistent (as shown in Figure 1).SnO 2/ C xn ythe nanostructure of/GN is characterized by high resolution transmission electron microscope (HR-TEM) further, as shown in Fig. 2 (c), and SnO 2nano particle is evenly dispersed on the surface of carbonitride.Clearly SnO can be found in the illustration of Fig. 2 (d) 2lattice fringe.Spacing of lattice is that the lattice fringe of 0.323nm and 0.230nm correspond to SnO respectively 2(110) and (200) crystal face.
In order to the structural change of the reducing degree and carbon nitride material that characterize graphene oxide, sample is carried out Fourier transform infrared spectroscopy test (as Fig. 3).As everyone knows, graphene oxide is at following infrared absorption peak: 1740cm -1place correspond to-COOH, at 1401cm -1correspond to O-H, at 1220cm -1correspond to C-OH, 827 and 1052cm -1correspond to O-C=O and C-O respectively, in addition, at 1620cm -1there is a SP at place 2the characteristic feature peak of C=C.In Fig. 3, at 617cm in the infrared spectrogram of three samples -1have an obvious infrared absorption peak, this is owing to the stretching vibration of Sn-O.Sample SnO in (b) figure 2/ DAMN/GO contains the infrared absorption peak of-COOH ,-CHO and O-H, and (c) figure sample SnO 2/ C xn ydo not detect in/GN, this is because the graphene oxide in sample is obtaining reduction after high-temperature process.In addition, sample SnO can be found 2/ DAMN/GO is at 2270cm -1there is very strong-C ≡ N peak, and at sample SnO 2/ C xn y/ GN and SnO 2/ C xn yin become very very weak, and at 1300cm -1place creates C-N peak, at 1630cm -1place creates C=N peak, and the formation having carbonitride after high temperature cabonization is described.Sample SnO 2/ C xn y/ GN and SnO 2/ C xn ycurve in 900cm -1~ 600cm -1absworption peak becomes than sample SnO 2/ DAMN/GO is more obvious, and this is caused by aromatic compound increases.Therefore, sample can form carbonitride conjugated conductive network through higher heat treatment temperature, and at high temperature graphite oxide more thoroughly can be reduced to Graphene.This consistent with AC impedance spectrogram result (as shown in Figure 6).
In order to obtain SnO 2/ C xn ythe content of tin oxide in/GN composite material, has carried out thermal weight loss test (as Fig. 4) to this sample.Known according to Fig. 4, composite material only has slight mass loss before 300 DEG C, illustrates that carbon in composite material and tin oxide still remain chemical stability to 300 DEG C of temperature in atmosphere.300-550 DEG C of mass loss is obvious, and this is owing to carbonitride and the aerial vigorous combustion reaction of Graphene.Finally, SnO is only had 2particle can be retained.According to SnO 2/ C xn ythe TGA curve of/GN, the tin oxide content in derived sample is about 38%.
Comprehensive above analysis can be inferred, the present invention successfully prepares SnO 2/ C xn y/ GN composite material.
Electrochemical property test
Mass ratio by 8: 1: 1 takes above-mentioned composite sample (active material), acetylene black, Kynoar (PVDF) (PVDF is dissolved in 1-METHYLPYRROLIDONE in advance), and three is uniformly mixed to form slurry; By slurry even application on Copper Foil.After pole piece puts into vacuum drying chamber 100 DEG C of dry 10h, being cut into diameter is that the thin slice of 16mm makes pole piece.Be to electrode with lithium metal, make CR2032 type button cell in the glove box being full of argon gas, barrier film adopts U.S. Celgard2400, and electrolyte adopts LiPF 6/ EC: DEC (1:1 volume ratio).Adopt the charge-discharge performance of LandCT2001A battery test system test sample, discharge and recharge final voltage is 0.005-2.5V.Cyclic voltammetry adopts the test of AmetekPARSTAT4000 electrochemical workstation, and sweep speed is 0.2mVs -1, voltage range 0.01-2.5V.
Fig. 5 is SnO 2/ C xn y, SnO 2/ DAMN/GO and SnO 2/ C xn y/ GN is at 100mAg -1current density under stable circulation performance and SnO 2/ C xn ythe coulombic efficiency figure of/GN.As shown in Figure 5, SnO 2/ C xn y, SnO 2/ DAMN/GO, SnO 2/ C xn ythe first charge-discharge specific capacity of/GN tri-samples is respectively 850.6/1811.3mAhg -1, 985.8/2338.8mAhg -1, 1164.1/2556.6mAhg -1.Three samples have a larger irreversible capacity loss in discharge process first, are respectively 53.0%, 57.8% and 54.4%, this formation owing to solid electrolyte film (SEI film) and SnO 2decomposition.SnO 2/ C xn y, SnO 2/ DAMN/GN, SnO 2/ C xn ythe capacity retention rate of/GN after 50 circulations (compared with second time) is respectively 16.5%, 54.1% and 69.4%.It should be noted that SnO 2/ C xn y/ GN sample special capacity fade after 100 circulations is little, still remains on 730mAhg -1left and right.
As shown in Figure 5, SnO 2/ C xn ythe coulombic efficiency of/GN sample all remains on about 100% except first twice, shows the electrochemical reversibility that this material is good.SnO 2/ C xn ythe good chemical property of/GN is owing to SnO 2nano particle being uniformly distributed (XRD and TEM proves) in carbonitride.In addition, not only contributed to the structure of conductive network by heat treatment, and graphene oxide can be made more thoroughly to reduce, both significantly can increase the conductivity of composite material.On the contrary, SnO 2/ C xn ythe capacity attenuation of sample quickly, this may be due to the dispersiveness of granules of stannic oxide in carbonitride is bad and material conductivity poor.
For proving the conductivity of three kinds of composite materials further, ac impedance measurement (as Fig. 6) is carried out to them.The AC impedance figure of Fig. 6 sample obtained by three different materials, AC impedance curve is the rectilinear(-al) of semicircle by high frequency region and low frequency range.Half circular diameter of high frequency region is less, and the resistance of sample is less.As can be seen from the figure, SnO 2/ C xn y/ GN has minimum resistance.This illustrate high temperature cabonization contribute to carbonitride conjugate network formation (consistent with Fourier's infrared test result, as shown in Figure 3), improve the conductivity of material.In addition, Graphene add the conductivity also substantially increasing material.
Fig. 7 is SnO 2/ C xn ythe rate charge-discharge cycle performance figure of/GN composite material.As seen from the figure, 100mAg is turned back to again through different current density discharge and recharge -1current density, it still can turn back to 750mAg than taking in -1left and right.Illustrate that the structure of material is not destroyed after high current charge-discharge, the stability of material is fine.
SnO in sum 2why-S/N-GNs composite material presents so excellent chemical property, returns its reason to mainly contain following 3 points: first, N doped graphene is coated on SnO 2nanoparticle size is peripheral, effectively inhibits SnO in cyclic process 2volumetric expansion problem; Secondly, introduce the diaminomaleonitrile containing greater activity group, after high temperature cabonization, cross-linked polymeric becomes the cancellated carbonitride of conjugation, while raising graphite oxide conductivity, also for the compound of graphene oxide and inorganic material provides more reaction active site, the chemical property of composite material is increased; In addition, SnO in course of reaction is conducive to adding of Graphene 2the dispersion of nano particle, can obtain the nano particle that particle size is less, can slow down the Volumetric expansion in embedding lithium/de-lithium process, promote ion transportation.
In order to study the energy storage mechnism of this composite material further, this composite material being assembled into battery and having carried out cyclic voltammetry (as shown in Figure 8).Can observe from Fig. 8 (a), near 0.6V, the irreversible reduction peak that weak is had in first time circulation, this peak does not occur in circulation below, and this formation owing to solid electrolyte film (SEI film) and tin oxide are decomposed into the process of metallic tin.This peak is corresponding with the discharge platform in Fig. 8 (b) first on discharge curve near 0.6V.As shown in formula (1):
SnO 2+4Li ++4e -→2Li 2O+Sn(1)
Reduction peak clearly near 0.22V and the oxidation peak near 0.54V respectively with the alloy reaction of tin, lithium and Sn from Li xremove relevant in Sn alloy.As shown in formula (2):
Sn+xLi ++xe -←→Li xSn(0≤x≤4.4)(2)
This paper is with SnCl 45H 2o, diaminomaleonitrile and graphite oxide are that the carbonitride combined oxidation tin material having three's advantage concurrently prepared by raw material through hydro-thermal and high-temperature process.Experimental data shows, this material list reveals excellent chemical property: at 100mAg -1current density under, constant current charge-discharge 100 specific capacities that circulate still can maintain 730mAhg -1left and right.This experimental technique is simple, gentle, economic environmental protection, for exploitation large-capacity and high-performance lithium ion battery opens a new path.

Claims (7)

1. for a composite material for cathode of lithium battery, it is characterized in that: adopt and be prepared from by the ratio of cyano-containing and amino organic substance, pink salt and graphite oxide three kinds of raw materials 4:6:1 in mass ratio.
2. a kind of composite material for cathode of lithium battery according to claim 1, is characterized in that: described cyano-containing and amino organic substance are diaminomaleonitrile.
3. a kind of composite material for cathode of lithium battery according to claim 1, is characterized in that: described pink salt is SnCl45H2O.
4. the preparation method of a kind of composite material for cathode of lithium battery according to claim 1, is characterized in that, comprise the steps:
(1) by graphite oxide ultrasonic disperse in distilled water, obtain graphene oxide solution, the solution obtained is labeled as solution A;
(2) solution A is heated to 30-60 DEG C, slowly adds diaminomaleonitrile under stirring, make it fully dissolve, the solution obtained is designated as solution B;
(3) under stirring, by SnCl after diaminomaleonitrile dissolves completely 45H 2o is dissolved in above-mentioned solution B;
(4) SnCl 45H 2after O dissolves completely, mixed liquor is made to react 8-20h under 120-180 DEG C of condition;
(5), after reaction, naturally room temperature is down to; Product is calcined more than 2 hours at 400-600 DEG C after centrifuge washing drying; SnO can be obtained 2/ C xn y/ GN composite material.
5. method according to claim 4, is characterized in that: described in step (1), graphene oxide solution concentration is 0.3-3.0mgmL -1.
6. method according to claim 4, is characterized in that: reaction described in step (4) is carried out in water heating kettle.
7. method according to claim 4, is characterized in that: described in step (5), calcining carries out under atmosphere of inert gases.
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CN108123126A (en) * 2017-12-20 2018-06-05 厦门紫阳科技产业发展有限公司 A kind of preparation method of high-capacity lithium ion cell stannic oxide/nitrogen-doped graphene composite negative pole material
CN109935824A (en) * 2017-12-15 2019-06-25 东莞市凯金新能源科技股份有限公司 A kind of expanded graphite negative electrode material and preparation method thereof loading cross acicular tin oxide
CN110052281A (en) * 2019-03-10 2019-07-26 天津大学 A kind of Lacking oxygen enriched in nitrogen doped stannum oxide and its preparation method and application
CN111540897A (en) * 2020-05-11 2020-08-14 中国科学院重庆绿色智能技术研究院 Preparation method of high-performance hollow three-dimensional tin-carbon lithium battery cathode material
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CN107634207A (en) * 2017-09-19 2018-01-26 大连海事大学 A kind of silicon mosaic redox graphene/graphite phase carbon nitride composite and its preparation and application
CN109935824A (en) * 2017-12-15 2019-06-25 东莞市凯金新能源科技股份有限公司 A kind of expanded graphite negative electrode material and preparation method thereof loading cross acicular tin oxide
CN109935824B (en) * 2017-12-15 2021-05-11 广东凯金新能源科技股份有限公司 Expanded graphite cathode material loaded with cross needle-shaped tin oxide and preparation method thereof
CN108123126A (en) * 2017-12-20 2018-06-05 厦门紫阳科技产业发展有限公司 A kind of preparation method of high-capacity lithium ion cell stannic oxide/nitrogen-doped graphene composite negative pole material
CN110052281A (en) * 2019-03-10 2019-07-26 天津大学 A kind of Lacking oxygen enriched in nitrogen doped stannum oxide and its preparation method and application
CN110052281B (en) * 2019-03-10 2021-11-05 天津大学 Oxygen vacancy enriched nitrogen doped tin oxide and preparation method and application thereof
CN111540897A (en) * 2020-05-11 2020-08-14 中国科学院重庆绿色智能技术研究院 Preparation method of high-performance hollow three-dimensional tin-carbon lithium battery cathode material
CN111540897B (en) * 2020-05-11 2021-08-06 中国科学院重庆绿色智能技术研究院 Preparation method of high-performance hollow three-dimensional tin-carbon lithium battery cathode material
CN111564321A (en) * 2020-05-27 2020-08-21 新昌县易纵新材料科技有限公司 Tin oxide-modified g-C3N4Electrode material of super capacitor and preparation method thereof
CN111564321B (en) * 2020-05-27 2023-01-13 新昌县易纵新材料科技有限公司 Tin oxide-modified g-C 3 N 4 Electrode material of super capacitor and preparation method thereof

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