CN102916187B - Method for preparing graphene/lithium stannate composite material of lithium battery - Google Patents
Method for preparing graphene/lithium stannate composite material of lithium battery Download PDFInfo
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- CN102916187B CN102916187B CN201210437006.6A CN201210437006A CN102916187B CN 102916187 B CN102916187 B CN 102916187B CN 201210437006 A CN201210437006 A CN 201210437006A CN 102916187 B CN102916187 B CN 102916187B
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- dimethyl formamide
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a method for preparing a cathode material, namely a lithium stannate/graphene composite material, of a lithium ion battery, wherein an Li2SnO3/graphene composite cathode material is prepared by chemically reducing and oxidizing graphene; graphene used as a steady carrier having good electrical conductivity is capable of effectively relieving volume expansion caused by charging and discharging and preventing the cohesion phenomenon; attenuation of the capacity of the electrode material is retarded; therefore, the capacity of the Li2SnO3 cathode material modified by graphene is far more than the theoretical capacity of the ordinary carbon material and higher than the cycle performance of pure-phase Li2SnO3. According to the graphene/lithium stannate composite material prepared by the invention, because of addition of graphene, the volume change caused by charging and discharging can be effectively relieved; the cohesion phenomenon in the event of carrying out lithium separating and inserting reaction can be inhibited; the electrode capacity of the material can be prevented from being rapidly attenuated; the initial irreversible capacity is reduced; therefore, the capacity of the graphene/lithium stannate cathode material is far more than the theoretical capacity of the ordinary carbon material and higher than the cycle performance of pure-phase Li2SnO3.
Description
Technical field
The invention belongs to the preparation method of the negative material of technical field of lithium batteries, be specifically related to a kind of preparation method of lithium ion battery cathode material lithium stannate/graphene composite material.
Background technology
Lithium ion battery applies one of power supply best with DEVELOPMENT PROSPECT in recent years.The key improving the chemical property of lithium ion battery seeks suitable electrode material, makes battery have sufficiently high storage lithium amount and good lithium deintercalation invertibity, to ensure the requirement of battery Large Copacity, high voltage and long circulation life.
At present, the domestic and international preparation for carbon based negative electrodes material and research are reported more, the commercial negative material of great majority is also based on carbon-based material, but the theoretical capacity of graphite material is only 372mAh/g, there is specific capacity low, first charge-discharge efficiency is low, and organic solvent such as to embed altogether at the deficiency, people are devoted to the height ratio capacity non-carbon negative material of development of new, and tin-based material receives the concern of people day by day with its distinctive height ratio capacity.Document " Journal of Alloysand Compounds ", 415,1-2 (2006) pp.229-23 discloses a kind of lithium stannate (Li
2snO
3) preparation method of material.The document adopts sol-gal process to prepare Li
2snO
3powder, it is with SnCl
45H
2o is presoma, take citric acid as complexing agent, synthesis Li
2snO
3powder.First by SnCl
45H
2o is dissolved in ethylene glycol solution, adds citric acid after stirring, after solution clarification, add Li
2cO
3be stirred to transparent obtained colloidal sol; Again obtained colloidal sol is put into drying box dry, to make colloidal sol crystallization; Then be placed on electrothermal furnace by the xerogel of solvent evaporated, heating makes it burn until completely; Again by the xerogel that obtains in Muffle furnace in temperature 400 DEG C of pre-burning 5h; Finally the above-mentioned substance obtained is obtained product at Muffle furnace in 700 DEG C of sintering 5h after grinding.Through constant current charge-discharge experiment test.Its first discharge capacity can reach 1080mAh/g, charging capacity 423mAh/g, first irreversible capacity 657mAh/g, coulombic efficiency is only 39.1% first, after 50 circulations, capacity keeps 380mAh/g (at current density 60mA/g, voltage range 0 ~ 1.0V).But method prepares pure phase Li described in document
2snO
3there is following shortcoming: adopt sol-gal process preparation more loaded down with trivial details, step is more, and Li
2snO
3the irreversible capacity first of electrode is larger.This is because tin is in charge and discharge cycles process, volume there occurs and expands and shrink, cause die break, structural breakdown, cause the destruction of electrode, decrease the cycle life of electrode, and it inserts easy " reunion " when lithium reacts de-, cause initial irreversible capacity to increase, finally cause capacity to reduce.
Summary of the invention
The technical problem solved
In order to avoid the deficiencies in the prior art part, the present invention proposes a kind of preparation method of lithium ion battery cathode material lithium stannate/graphene composite material, adopts graphene oxide reducing process to prepare Graphene/lithium stannate composite material.
Technical scheme
A preparation method for lithium ion battery cathode material lithium stannate/graphene composite material, is characterized in that step is as follows:
Step 1: the graphene oxide and the Li that by mass ratio are 1:1 ~ 1:5
2snO
3be dissolved in 250ml ~ 400ml N respectively, in N-dimethyl formamide DMF, ultrasonicly make the two disperse respectively, obtain containing Li
2snO
3n, N-dimethyl formamide DMF solution and containing the N of graphene oxide, N-dimethyl formamide DMF solution;
Step 2: will containing Li
2snO
3n, N-dimethyl formamide DMF solution joins the N containing graphene oxide, in N-dimethyl formamide DMF solution, stirs; Add again 2ml ~ 4ml, concentration be 30% hydrazine hydrate N
2h
4h
2o, then at 85-95 DEG C of stirred in water bath reaction 18h-24h, solution is cooled to room temperature when yellow green becomes black;
Step 3: solution step 2 obtained filters, and uses chloroform CCl
3washing, obtains Li after drying under room temperature
2snO
3/ graphene composite material.
Beneficial effect
The preparation method of a kind of lithium ion battery cathode material lithium stannate/graphene composite material that the present invention proposes, adopts the method for electronation graphene oxide to prepare Li
2snO
3/ graphene composite negative pole, Graphene, as a kind of stable carrier with satisfactory electrical conductivity, can alleviate the volumetric expansion caused by discharge and recharge effectively, avoids " reunion " phenomenon, slow down the decay of electrode material capacity, make the Li of graphene modified
2snO
3the capacity of negative material much larger than the theoretical capacity of common material with carbon element, and higher than pure phase Li
2snO
3cycle performance.
Graphene prepared by the present invention/lithium stannate composite material, by lithium stannate with there is elasticity, conductivity and the Graphene compound of stable performance, cushioning its change in volume, will be the effective way improving stability of material.Due to adding of Graphene, change in volume caused when effectively can alleviate discharge and recharge, suppress in de-" reunion " phenomenon of inserting when lithium reacts, material electrodes capacity attenuation can be avoided too fast, reduce initial irreversible capacity, make the theoretical capacity of capacity much larger than common material with carbon element of Graphene/lithium stannate negative material, and higher than pure phase Li
2snO
3cycle performance.
Accompanying drawing explanation
Fig. 1: be product in embodiment 3 under current density 60mA/g (0-2.0V) condition, front twice charging and discharging curve figure;
Fig. 2: be the cycle performance figure of product under current density 60mA/g (0-2.0V) condition in embodiment 3;
Fig. 3: the TEM figure being Graphene/lithium stannate in embodiment 3.
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Embodiment 1:
Be graphene oxide and the Li of 1:2 by mass ratio
2snO
3be dissolved in 500ml N respectively, in N-dimethyl formamide (DMF), ultrasonicly make the two disperse respectively, will containing Li
2snO
3n, N-dimethyl formamide (DMF) solution slowly joins the N of graphene oxide, in N-dimethyl formamide (DMF) solution, stirs, and adds a certain amount of certain density hydrazine hydrate (N
2h
4h
2o), in 95 DEG C of stirred in water bath reaction 24h, solution becomes black from yellow green, when solution is cooled to room temperature, by sample filtering, with chloroform (CCl
3) wash three times, namely obtain the composite sample needed for us under room temperature after drying.
Product in embodiment 1 is assembled into CR2016 button cell, is to electrode with lithium sheet (Φ=16 purity >99.9%), with polypropylene porous film (Φ=18) for barrier film, with LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (VEC:VDMC=1:1) as electrolyte, CR2016 battery completes in the glove box being full of argon gas.Electrode forms with the tape casting membrane, slurry used is the active material of 65% (mass percent), the PVDF solution of 20%, conductive black, the 1-Methyl-2-Pyrrolidone (NMP) of 15% mix, and the substrate of electrode film is metal copper foil.Under current density 60mA/g condition, carry out charge-discharge performance test, charging/discharging voltage scope is 0.05-2.0V.The discharge capacity first recording product can reach 1527.3mAh/g, initial charge capacity 928.3mAh/g, and after 50 circulations, discharge capacity keeps about 582.2mAh/g.And at current density 60mA/g, when charging/discharging voltage scope is 0-1.0V, after 50 circulations, discharge capacity keeps about 450mAh/g.
Embodiment 2:
Be graphene oxide and the Li of 1:3 by mass ratio
2snO
3be dissolved in 500ml N respectively, in N-dimethyl formamide (DMF), ultrasonicly make the two disperse respectively, will containing Li
2snO
3n, N-dimethyl formamide (DMF) solution slowly joins the N of graphene oxide, in N-dimethyl formamide (DMF) solution, stirs, and adds a certain amount of certain density hydrazine hydrate (N
2h
4h
2o), in 95 DEG C of stirred in water bath reaction 5h, solution becomes black from yellow green, when solution is cooled to room temperature, by sample filtering, with chloroform (CCl
3) wash three times, namely obtain the composite sample needed for us under room temperature after drying.
Product in embodiment 2 is assembled into CR2016 button cell (method is with embodiment 1).Under current density 60mA/g condition, carry out charge-discharge performance test, charging/discharging voltage scope is 0.05-2.0V.The discharge capacity first recording product can reach 1427.1mAh/g, charging capacity 1021mAh/g, and after 50 circulations, discharge capacity keeps about 550mAh/g.And at current density 60mA/g, when charging/discharging voltage scope is 0-1.0V, after 50 circulations, discharge capacity keeps about 430mAh/g.
Embodiment 3:
Be graphene oxide and the Li of 1:5 by mass ratio
2snO
3be dissolved in 500ml DMF (DMF) respectively, ultrasonicly make the two disperse respectively, will containing Li
2snO
3dMF (DMF) solution slowly join the N of graphene oxide, in N-dimethyl formamide (DMF) solution, stir, add a certain amount of certain density hydrazine hydrate (N
2h
4h
2o), in 95 DEG C of stirred in water bath reaction 24h, solution becomes black from yellow green, when solution is cooled to room temperature, by sample filtering, with chloroform (CCl
3) wash three times, namely obtain the composite sample needed for us under room temperature after drying.
Product in embodiment 3 is assembled into CR2016 button cell (method is with embodiment 1).Under current density 60mA/g condition, carry out charge-discharge performance test, charging/discharging voltage scope is 0.05-2.0V.The discharge capacity first recording product can reach 1527.3mAh/g, initial charge capacity 983.3mAh/g, and after 50 circulations, discharge capacity keeps about 576.5mAh/g.And at current density 60mA/g, when charging/discharging voltage scope is 0-1.0V, after 50 circulations, discharge capacity keeps about 450mAh/g.
From the test result of above embodiment, at current density 60mA/g, charging/discharging voltage scope is under the condition of 0.05-2.0V, and the first charge-discharge capacity of product of the present invention is higher than the Li of sol-gal process
2snO
3charge/discharge capacity (bibliographical information see in background technology).Capacity after 50 circulations is kept above the Li of collosol and gel
2snO
3respective volume.Illustrate that lithium stannate/Graphene is good lithium ion battery negative material.
Claims (1)
1. a preparation method for graphene/lithium stannate composite material of lithium battery, is characterized in that step is as follows:
Step 1: the graphene oxide and the Li that by mass ratio are 1:1 ~ 1:5
2snO
3be dissolved in 250ml ~ 400ml N respectively, in N-dimethyl formamide DMF, ultrasonicly make the two disperse respectively, obtain containing Li
2snO
3n, N-dimethyl formamide DMF solution and containing the N of graphene oxide, N-dimethyl formamide DMF solution;
Step 2: will containing Li
2snO
3n, N-dimethyl formamide DMF solution joins the N containing graphene oxide, in N-dimethyl formamide DMF solution, stirs; Add again 2ml ~ 4ml, concentration be 30% hydrazine hydrate N
2h
4h
2o, then at 85-95 DEG C of stirred in water bath reaction 18h-24h, solution is cooled to room temperature when yellow green becomes black;
Step 3: solution step 2 obtained filters, and uses chloroform CCl
3washing, obtains Li after drying under room temperature
2snO
3/ graphene composite material.
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| CN107180965B (en) * | 2017-07-10 | 2019-08-30 | 浙江美都墨烯科技有限公司 | A kind of nano-scale lithium iron phosphate/graphene composite material and its preparation method and application |
| CN108232159B (en) * | 2018-01-05 | 2020-09-04 | 济南大学 | graphene/CuMn 2O4 composite electrode material, and preparation method and application thereof |
| CN108807945A (en) * | 2018-07-27 | 2018-11-13 | 上海工程技术大学 | Redox graphene/stannate anode material of lithium-ion battery and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Hydrothermal derived Li2SnO3/C composite as negative electrode materials for lithium-ion batteries;Qiufen Wang等;《Applied Surface Science》;20120401;第258卷;第6923-6929页 * |
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