CN103107313B - Tin-based oxide/graphene composite material,preparation method and application thereof - Google Patents
Tin-based oxide/graphene composite material,preparation method and application thereof Download PDFInfo
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- CN103107313B CN103107313B CN201310029866.0A CN201310029866A CN103107313B CN 103107313 B CN103107313 B CN 103107313B CN 201310029866 A CN201310029866 A CN 201310029866A CN 103107313 B CN103107313 B CN 103107313B
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Abstract
The invention discloses a tin-based oxide/graphene composite material, a preparation method and an application thereof. The composite mateiral comprises a nanoscale tin-based oxide and graphene, wherein the nanoscale tin-based oxide has a general formula of MsnO3, and M is Mg, Co, Ca or Zn. The tin-based oxide in the composite material can be uniformly distributed due to dispersion and bearing effects of graphene, the composite material has small particle size, the cyclical stability of the tin-based oxide can be effectively improved in a charge and discharge process, and the composite material can be used as a lithium ion battery cathode material. The invention further discloses a preparation method of the composite material in one step at low temperature. The preparation method has the advantages of simplicity in process, low cost, short cycle and low energy consumption and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to lithium ion battery field of compound material, be specifically related to a kind of tin-based oxide/graphene composite material and its preparation method and application.
Background technology
Lithium ion battery has the advantages such as operating voltage is high, energy density is large, security performance is good, is therefore used widely in the portable type electronic products such as digital camera, mobile phone and notebook computer, also has application prospect for electric bicycle and electric automobile.Current commercial lithium ion battery generally adopts carbon based negative electrodes material, and as graphite, although this material stability is higher, theoretical capacity only has 372mAhg
-1.
Compared with material with carbon element, some transition metal oxide has higher theoretical capacity, as Fe
2o
3theoretical capacity up to 1000mAhg
-1.This kind of transition metal oxide has a general character: contained oxygen with lithium metal, reversible reaction can occur, and this reaction provides reversible capacity, and the transition metal discord lithium generation alloying of embedding lithium formation first/taking off alloying reaction, its process is:
M’
xO
y+2y?Li→x?M’+y?Li
2O
Although this reaction can provide higher capacity, because change in volume in removal lithium embedded process is comparatively large, cause the rapid decay of capacity.At present, the method effectively slowing down capacity rapid decay is generally that transition metal oxide and other basis material are carried out compound, and comparatively ideal basis material is material with carbon element.In various material with carbon element, Graphene, because its high conductivity, high mechanical strength, large specific area and porosity, is ideal basis material.
The report preparing composite material in prior art using Graphene as basis material is existing a lot, as disclosed a kind of transition metal oxide/graphene composite material in Chinese patent application CN201110083375.5, be made up of nanocrystalline transition metal oxide and Graphene, described transition metal oxide is MnO, Fe
2o
3, Cr
2o
3, Cu
2o, CuO or V
2o
5; In this composite material transition metal oxide due to Graphene dispersion and carrying effect can be uniformly distributed and granularity is little, effectively can improve the stability of transition metal oxide in charge and discharge process and cyclical stability.A kind of transition metal oxide/graphene nanometer composite electrode material used for lithium battery and preparation method thereof is disclosed in Chinese patent application CN201010237027.4, it is the transition metal oxide of Graphene or graphene oxide modification, transition metal oxide is connected in the mode of physically encapsulation or chemical bonding with between Graphene or graphene oxide, adopt the one in following method: be 1. 0.01: 100 to 50: 100 Homogeneous phase mixing in a solvent by weight by the precursor prepared needed for transition metal oxide and Graphene (or graphene oxide), in uniform temperature, nanometer combined electrode material is obtained by reacting under pressure, 2. be in a solvent fully to mix at 0.01: 100 to 50: 100 by weight by Graphene (or graphene oxide) and transition metal oxide, drying obtains nanometer combined electrode material, preparation method is easy, easy to operate, is applicable to large-scale production, and obtained electrode material has higher lithium ion and the conductivity of electronics, and the lithium battery specific capacity of assembling is high, good cycle, is suitable for electrode material of lithium battery.Disclose a kind of tin-base complex oxide/graphene composite material in Chinese patent application CN201210254843.5, be made up of nanoscale tin-base complex oxide and Graphene, the general formula of described tin-base complex oxide is M
2snO
4, wherein M is Mg, Co, Ca or Zn; In this composite material tin-base complex oxide due to Graphene dispersion and carrying effect can be uniformly distributed and granularity is little, effectively can improve the stability of tin-base complex oxide in charge and discharge process and cyclical stability, can be used as lithium ion battery negative material.
Therefore, development of metallic oxide/graphene composite material has broad application prospects.
Summary of the invention
The invention provides a kind of electrochemical stability and the good tin-based oxide/graphene composite material of cyclical stability.
Present invention also offers a kind of preparation method of tin-based oxide/graphene composite material, the method technique is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production.
The present invention finds that (general formula is MSnO by tin-based oxide
3, wherein M is Mg, Co, Ca or Zn) and Graphene compound, can be used to the chemical property, particularly cyclical stability that improve tin-based oxide.
A kind of tin-based oxide/graphene composite material, be made up of nanoscale tin-based oxide and Graphene (G), the general formula of described tin-based oxide is MSnO
3, wherein M is Mg, Co, Ca or Zn.
In order to improve the application performance of composite material further, in described composite material, the weight percentage of Graphene is preferably 0.4% ~ 20%, and more preferably 3.9% ~ 13.8%.
The particle diameter of tin-based oxide is less, more easily cover and be loaded on Graphene, the electrochemical stability performance of composite material is better, and therefore the present invention selects nanoscale tin-based oxide, preferably, the particle size of described nanoscale tin-based oxide is 50 nanometer ~ 100 nanometers; The nano particle of this size range can be prepared easily, especially adopts preparation method of the present invention to be easy to prepare.Further preferably, the particle of described nanoscale tin-based oxide is cuboid, most preferably is cube shaped, and the electrochemical stability of material and cyclical stability can be further enhanced.
Preferably, in described composite material, nanoscale tin-based oxide is dispersed; Electrochemical stability and cyclical stability can be further enhanced.
The preparation method of described tin-based oxide/graphene composite material, comprises the following steps:
1) by being that 1:1 is dissolved in deionized water or organic solvent containing the salt of tetravalence Sn and divalence M salt by Sn and M mol ratio, obtaining the solution that Sn and M total concentration is 0.01mol/L ~ 0.1mol/L, then adding GO, obtaining mixed solution through ultrasonic disperse;
The addition of described GO is tin-based oxide MSnO
31% ~ 50% of theoretical weight, more preferably 10% ~ 40%;
Wherein M is Mg, Co, Ca or Zn;
2) pH value is adjusted to 8 ~ 12(preferably 9 ~ 11 by adding alkaline conditioner in the mixed solution of step 1)), 100 DEG C ~ 250 DEG C are warming up to after sealing, react after 12 hours ~ 48 hours and cool, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying, obtains dried product;
3) by step 2) at dried product 200 DEG C in an inert atmosphere ~ 500 DEG C heat treatment within 1 hour ~ 10 hours, obtain tin-based oxide/graphene composite material.
Do not need in the method to use reducing agent, in the basic conditions, graphene oxide becomes Graphene by solvothermal.
The described salt containing tetravalence Sn is the hydrate of the tetrafluoride of tin, the tetrachloride of tin, potassium stannate, sodium stannate or any one salt described.
Described divalence M salt is the hydrate of the fluoride of divalence M, the chloride of divalence M, the nitrate of divalence M, the sulfate of divalence M, the oxalates of divalence M, the acetate of divalence M or any one salt described.
Described organic solvent is ethanol, methyl alcohol, ethylene glycol, n-butyl alcohol, DMF, pyridine, ethylenediamine, benzene or toluene.
Described alkaline conditioner is mainly used to adjust ph to 8 ~ 12, and addition is depending on required pH, and concentration is without considered critical, and effect has two aspects: (1) promotes the hydrolysis of metal ion and the formation of tin-based oxide; (2) reduction of accelerating oxidation Graphene, can select the aqueous solution of ammoniacal liquor, hydrazine hydrate, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
Step 2) in, preferred in 190 DEG C ~ 240 DEG C reactions cooling after 20 hours ~ 32 hours further; Reaction temperature is high, and the time is long, and tin-based oxide is easily formed, and graphene oxide is easily reduced into Graphene, but little on particle size impact.
In step 3), preferably further to cool after 2 hours ~ 4 hours 200 DEG C ~ 400 DEG C heat treatments; Reaction temperature is high, and the time is long, and tin-based oxide is easily formed, and the remaining oxy radical on Graphene can be removed further, improves electrochemical stability and the cycle performance of composite material further, but little on particle size impact.
The temperature of described cooling not strict restriction, based on adequate operation, generally can be cooled to the ambient temperature of 15 DEG C ~ 30 DEG C.
Described tin-based oxide/graphene composite material can be used as lithium ion battery negative material.
Compared with prior art, tool of the present invention has the following advantages:
1, the present invention adopts one-step method at low-temperature growth tin-based oxide/graphene composite material, has that technique is simple, cost is low, the cycle is short, energy consumption is low and the advantage such as applicable suitability for industrialized production.
2, due to dispersion and the carrying effect of Graphene, in gained composite material, tin-based oxide granularity is little, and diameter is 50 nanometer ~ 100 nanometers, and distribution is more even.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained CoSnO
3the X ray diffracting spectrum of/graphene composite material.
Fig. 2 is embodiment 1 gained CoSnO
3the stereoscan photograph of/graphene composite material;
Fig. 3 is embodiment 1 gained CoSnO
3/ graphene composite material and pure CoSnO
3chemical property figure.
Embodiment
Embodiment 1
Be the SnCl of 1:1 by mol ratio
45H
2o and CoCl
26H
2o is dissolved in deionized water, is mixed with 80 milliliters of Sn
4+and Co
2+total concentration is the solution of 0.01mol/L, then adds 36 milligrams of GO and obtain mixed solution; The capacity that is placed in by mixed solution is in the autoclave (compactedness 80%, percent by volume) of 100 milliliters, then with the KOH aqueous solution of 6mol/L, pH value is adjusted to 11, is then sealed by reactor, reacts 28 hours, naturally cool to room temperature at 200 DEG C; Collect solid reaction product, by product through deionized water and the washing of absolute ethyl alcohol alternate repetition, dry, (main component is CoSnO to obtain dried product
3/ graphene composite material, wherein, Graphene has abundant residues oxy radical); Again by the heat treatment 4 hours at 300 DEG C in nitrogen atmosphere of dried product, obtain 0.104g CoSnO
3/ graphene composite material, wherein, the weight percentage of Graphene is 13.8%.
The X ray diffracting spectrum of the composite material of gained and stereoscan photograph are respectively as Fig. 1 and Fig. 2, and wherein the diffraction maximum of X ray all can be summed up as CoSnO
3, the diffraction maximum of Graphene can not be found out from X ray diffracting spectrum, Graphene is described by CoSnO
3granular composite.Can be clear that the composite material of gained is CoSnO from ESEM
3/ graphene composite material, wherein CoSnO
3particle size is nanoscale, is 50 nanometer ~ 100 nanometers, and in cube shaped, and distribution is more even.
Respectively with gained CoSnO
3/ graphene composite material, dried product and pure nano Co SnO
3(its particle diameter is 50 nanometer ~ 100 nanometers; Pure nano Co SnO
3the i.e. material of not graphene-containing, adopts CoSnO
3prepared by/Graphene same method, difference does not add graphene oxide in building-up process, and other conditions are identical) carry out electrochemical property test (constant current charge-discharge within the scope of certain voltage) as lithium ion battery negative material, gained CoSnO
3/ G composite material and pure nano Co SnO
3chemical property figure as Fig. 3, constant current charge-discharge (current density 50mAg
-1, voltage range 0.005 ~ 3V) test show, when cycle-index is 1, CoSnO
3the capacity of/G composite material is 750mAhg
-1, when cycle-index is 20, CoSnO
3the capacity of/G composite material is only reduced to 526mAhg
-1; And cycle-index is when being 1, pure nano Co SnO
3capacity be 792mAhg
-1, when cycle-index is 20, pure nano Co SnO
3capacity reduce rapidly and be only 397mAhg
-1; When cycle-index is 1, the capacity of dried product is 672mAhg
-1, when cycle-index is 20, the capacity of dried product is reduced to 439mAhg
-1; Visible and pure nano Co SnO
3compare with dried product, CoSnO
3the cyclical stability of/G composite material significantly improves, and electrochemical stability is good.
Embodiment 2
Be the SnCl of 1:1 by mol ratio
45H
2o and Ca (CH
3cOO)
2h
2o is dissolved in n-butyl alcohol, is mixed with 80 milliliters of Sn
4+and Ca
2+total concentration is the solution of 0.04mol/L, then adds 100 milligrams of GO and obtain mixed solution; The capacity that is placed in by mixed solution is in the autoclave (compactedness 80%, percent by volume) of 100 milliliters, with 25wt% ammoniacal liquor, pH value is adjusted to 9, is then sealed by reactor, reacts 32 hours, naturally cool to room temperature at 190 DEG C; Collect solid reaction product, by product through deionized water and the washing of absolute ethyl alcohol alternate repetition, dry, (main component is CaSnO to obtain dried product
3/ graphene composite material, wherein, Graphene has abundant residues oxy radical); Again by the 350 DEG C of heat treatment 2.5 hours in argon atmospher of dried product, obtain 0.37g CaSnO
3/ graphene composite material, wherein, the weight percentage of Graphene is 10.8%.
Can find out that the composite material of gained is CaSnO from the X ray diffracting spectrum of the composite material of gained and stereoscan photograph
3/ graphene composite material, wherein CaSnO
3particle size is nanoscale, is 50 nanometer ~ 100 nanometers, and in cube shaped, and distribution is more even.
Respectively with gained CaSnO
3/ G composite material, dried product and pure nanometer CaSnO
3(its particle diameter is 50 nanometer ~ 100 nanometers; Pure nanometer CaSnO
3the i.e. material of not graphene-containing, adopts CaSnO
3/ G same method prepare, difference does not add graphene oxide in building-up process, and other conditions are identical) carry out electrochemical property test as lithium ion battery negative material, method of testing with embodiment 1, constant current charge-discharge (current density 50mAg
-1, voltage range 0.005 ~ 3V) and test is when showing that cycle-index is 1, CaSnO
3the capacity of/G composite material is 775mAhg
-1, when cycle-index is 20, CaSnO
3the capacity of/G composite material is only reduced to 543mAhg
-1; And cycle-index is when being 1, pure nanometer CaSnO
3capacity be 801mAhg
-1, when cycle-index is 20, pure nanometer CaSnO
3capacity reduce rapidly and be only 412mAhg
-1; When cycle-index is 1, the capacity of dried product is 686mAhg
-1, when cycle-index is 20, the capacity of dried product is reduced to 435mAhg
-1; Visible and pure nanometer CaSnO
3compare with dried product, CaSnO
3the cyclical stability of/G composite material significantly improves, and electrochemical stability is good.
Embodiment 3
Be the K of 1:1 by mol ratio
2snO
33H
2o and MgSO
47H
2o is dissolved in absolute ethyl alcohol, is mixed with 80 milliliters of SnO
3 2-and Mg
2+total concentration is the solution of 0.06mol/L, then adds 92 milligrams of GO and obtain mixed solution; The capacity that is placed in by mixed solution is in the autoclave (compactedness 80%, percent by volume) of 100 milliliters, with the NaOH aqueous solution of 6mol/L, pH value is adjusted to 10, is then sealed by reactor, reacts 24 hours, naturally cool to room temperature at 220 DEG C; Collect solid reaction product, by product through deionized water and the washing of absolute ethyl alcohol alternate repetition, dry, (main component is MgSnO to obtain dried product
3/ graphene composite material, wherein, Graphene has abundant residues oxy radical); Again by the heat treatment 3 hours at 400 DEG C in blanket of nitrogen of dried product, obtain 0.495g MgSnO
3/ graphene composite material, wherein, the weight percentage of Graphene is 7.5%.
Can find out that the composite material of gained is MgSnO from the X ray diffracting spectrum of the composite material of gained and stereoscan photograph
3/ graphene composite material, wherein MgSnO
3particle size is nanoscale, is 50 nanometer ~ 100 nanometers, and in cube shaped, and distribution is more even.
Respectively with gained MgSnO
3/ G composite material, dried product and pure nanometer MgSnO
3(its particle diameter is 50 nanometer ~ 100 nanometers; Pure nanometer MgSnO
3the i.e. material of not graphene-containing, adopts MgSnO
3/ G same method prepare, difference does not add graphene oxide in building-up process, and other conditions are identical) carry out electrochemical property test as lithium ion battery negative material, method of testing with embodiment 1, constant current charge-discharge (current density 50mAg
-1, voltage range 0.005 ~ 3V) test show, MgSnO
3the capacity of/G composite material is 741mAhg
-1, when cycle-index is 20, MgSnO
3the capacity of/G composite material is only reduced to 531mAhg
-1; And cycle-index is when being 1, pure nanometer MgSnO
3capacity be 811mAhg
-1, when cycle-index is 20, pure nanometer MgSnO
3capacity reduce rapidly and be only 340mAhg
-1; When cycle-index is 1, the capacity of dried product is 661mAhg
-1, when cycle-index is 20, the capacity of dried product is reduced to 413mAhg
-1; Visible and pure nanometer MgSnO
3compare with dried product, MgSnO
3the cyclical stability of/G composite material significantly improves, and electrochemical stability is good.
Embodiment 4
Be the Na of 1:1 by mol ratio
2snO
33H
2o and ZnCl
2be dissolved in benzene, be mixed with 80 milliliters of SnO
3 2-and Zn
2+total concentration is the solution of 0.1mol/L, then adds 93 milligrams of GO and obtain mixed solution; The capacity that is placed in by mixed solution is in the autoclave (compactedness 80%, percent by volume) of 100 milliliters, with 85wt% hydrazine hydrate aqueous solution, pH value is adjusted to 11, is then sealed by reactor, reacts 20 hours, then naturally cool to room temperature at 240 DEG C; Collect solid reaction product, by product through deionized water and the washing of absolute ethyl alcohol alternate repetition, dry, (main component is ZnSnO to obtain dried product
3/ graphene composite material, wherein, Graphene has abundant residues oxy radical); Again by the heat treatment 2 hours at 200 DEG C in helium-atmosphere of dried product, obtain 0.965g ZnSnO
3/ graphene composite material, wherein, the weight percentage of Graphene is 3.9%.
Can find out that the composite material of gained is ZnSnO from the X ray diffracting spectrum of the composite material of gained and stereoscan photograph
3/ graphene composite material, wherein ZnSnO
3particle size is nanoscale, is 50 nanometer ~ 100 nanometers, and in cube shaped, and distribution is more even.
Respectively with gained ZnSnO
3/ G composite material, dried product and pure nanometer ZnS nO
3(its particle diameter is 50 nanometer ~ 100 nanometers; Pure nanometer ZnS nO
3the i.e. material of not graphene-containing, adopts ZnSnO
3/ G same method prepare, difference does not add graphene oxide in building-up process, and other conditions are identical) carry out electrochemical property test as lithium ion battery negative material, method of testing with embodiment 1, constant current charge-discharge (current density 50mAg
-1, voltage range 0.005 ~ 3V) test show, when cycle-index is 1, ZnSnO
3the capacity of/G composite material is 765mAhg
-1, when cycle-index is 20, ZnSnO
3the capacity of/G composite material is only reduced to 538mAhg
-1; And cycle-index is when being 1, pure nanometer ZnS nO
3capacity be 788mAhg
-1, when cycle-index is 20, pure nanometer ZnS nO
3capacity reduce rapidly and be only 292mAhg
-1; When cycle-index is 1, the capacity of dried product is 677mAhg
-1, when cycle-index is 20, the capacity of dried product is reduced to 426mAhg
-1; Visible and pure nanometer ZnS nO
3compare, ZnSnO
3the cyclical stability of/G composite material significantly improves, and electrochemical stability is good.
Claims (7)
1. tin-based oxide/graphene composite material, is characterized in that, is made up of nanoscale tin-based oxide and Graphene, and the general formula of described tin-based oxide is MSnO
3, wherein M is Mg, Co, Ca or Zn;
In described composite material, the weight percentage of Graphene is 3.9% ~ 13.8%;
The particle size of described nanoscale tin-based oxide is 50 nanometer ~ 100 nanometers, in cube shaped;
The preparation method of described tin-based oxide/graphene composite material, comprises the following steps:
1) by being that 1:1 is dissolved in deionized water or organic solvent containing the salt of tetravalence Sn and divalence M salt by Sn and M mol ratio, obtaining the solution that Sn and M total concentration is 0.01 mol/L ~ 0.1 mol/L, then adding GO, obtaining mixed solution through ultrasonic disperse;
The addition of described GO is tin-based oxide MSnO
31% ~ 50% of theoretical weight;
Wherein M is Mg, Co, Ca or Zn;
2) by step 1) mixed solution in add alkaline conditioner pH value be adjusted to 8 ~ 12, be warming up to 100 DEG C ~ 250 DEG C after sealing, react after 12 hours ~ 48 hours and cool, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, dry, obtain dried product;
3) by step 2) at dried product 200 DEG C in an inert atmosphere ~ 500 DEG C heat treatment within 1 hour ~ 10 hours, obtain tin-based oxide/graphene composite material.
2. tin-based oxide/graphene composite material according to claim 1, is characterized in that, in described composite material, nanoscale tin-based oxide is dispersed.
3. tin-based oxide/graphene composite material according to claim 1, is characterized in that, the described salt containing tetravalence Sn is the hydrate of the tetrafluoride of tin, the tetrachloride of tin, potassium stannate, sodium stannate or any one salt described;
Described divalence M salt is the hydrate of the fluoride of divalence M, the chloride of divalence M, the nitrate of divalence M, the sulfate of divalence M, the oxalates of divalence M, the acetate of divalence M or any one salt described.
4. tin-based oxide/graphene composite material according to claim 1, is characterized in that, described organic solvent is ethanol, methyl alcohol, ethylene glycol, n-butyl alcohol, DMF, pyridine, ethylenediamine, benzene or toluene.
5. tin-based oxide/graphene composite material according to claim 1, is characterized in that, described alkaline conditioner is ammoniacal liquor, the aqueous solution of hydrazine hydrate, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
6. tin-based oxide/graphene composite material according to claim 1, is characterized in that, described inert atmosphere is nitrogen, argon gas or helium.
7. tin-based oxide/graphene composite material according to claim 1 and 2 is as the application in lithium ion battery negative material.
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| CN105449177B (en) * | 2015-11-30 | 2018-02-06 | 中南大学 | A kind of porous cube of ZnSnO for sodium-ion battery3@graphene negative materials and preparation method thereof |
| CN105633383B (en) * | 2016-03-16 | 2017-12-29 | 武汉理工大学 | CoSnO in the pipe that carbon is supported3Grain structure material and its preparation method and application |
| CN107799748A (en) * | 2017-10-23 | 2018-03-13 | 天津师范大学 | A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application |
| CN108817413B (en) * | 2018-05-04 | 2021-07-20 | 同济大学 | Preparation of CoSnO3Method for @ Au amorphous nano cube |
| CN108539184A (en) * | 2018-05-15 | 2018-09-14 | 肇庆益晟商贸有限公司 | A kind of modified graphene composite lithium ion battery cathode material and preparation method thereof |
| US10882029B1 (en) | 2019-10-08 | 2021-01-05 | King Fahd University Of Petroleum And Minerals | Graphene oxide and cobalt tin oxide nanocomposite and method of use |
| CN111554901B (en) * | 2020-05-11 | 2021-08-24 | 吉林中溢炭素科技有限公司 | Nano hollow SnO2-graphene lithium ion battery cathode material and preparation method thereof |
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| CN101927979A (en) * | 2010-08-03 | 2010-12-29 | 复旦大学 | Stannic oxide/ graphene nano composite as well as preparation method and application thereof |
| CN102760885A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Tin-base complex oxide/graphene composite material, and preparation method and application thereof |
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| A novel tin-based nanocomposite oxide as negative-electrode materials for li-ion batteries;Feng Huang等;《Materials Letters》;20030731;第57卷(第22-23期);第3341-3345页 * |
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