CN102227019A - Method for preparing tin-carbon composite material for cathode of lithium ion battery - Google Patents
Method for preparing tin-carbon composite material for cathode of lithium ion battery Download PDFInfo
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- CN102227019A CN102227019A CN2011101323266A CN201110132326A CN102227019A CN 102227019 A CN102227019 A CN 102227019A CN 2011101323266 A CN2011101323266 A CN 2011101323266A CN 201110132326 A CN201110132326 A CN 201110132326A CN 102227019 A CN102227019 A CN 102227019A
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Abstract
The invention provides a method for preparing a tin-carbon composite material for a cathode of a lithium ion battery in situ by using a so-gel method, comprising the following steps: dissolving stannous chloride in a fructose solution, heating to 75-90 DEG C and stirring at the condition of heat preservation until the moisture is evaporated; drying for 2-4 hours at the temperature of 110-130 DEG C; heating the dried product to 170-230 DEG C for about 2 hours in an inert atmosphere; heating to 400-700 DEG C for 2 hours; and cooling to obtain the tin-carbon composite material, wherein the mole ratio of the fructose to the stannous chloride dehydrate is 1: (0.4-1.6). The method is simple, the raw material cost is low, the specific capacity of the prepared tin-carbon composite material is high and the cycle performance is good.
Description
Technical field
The present invention relates to a kind of used as negative electrode of Li-ion battery material and preparation method thereof, particularly relate to a kind of used as negative electrode of Li-ion battery nanometer tin carbon composite and this preparation methods.
Background technology
Extensive use and fast development along with various portable electric appts and electric automobile, lithium ion battery is with its operating voltage height, energy density is big, have extended cycle life, advantages such as self-discharge rate is low, environmental protection, being widely used in portable electronics such as laptop computer, video camera, mobile communication, and beginning is obtaining application aspect the energy storage of hybrid vehicle, electric automobile, solar energy and wind energy.
The commercial lithium ion battery negative material of main flow is a graphitized carbon material at present, and theoretical capacity 372mAh/g can't satisfy people to the high performance demand of lithium ion battery.Metal Sn since its high theoretical specific capacity 992mAh/g caused people's very big concern, yet the challenge that faces now be metal Sn in the lithium ion battery charge and discharge process, have volumetric expansion, problems such as gathering, cause electrically contacting variation, the decline of circulation volume, the lost of life.In order to address these problems, nano level metal tin or tin compound are accommodated in the duct of porous carbon, solve volumetric expansion and the contraction problem of metallic tin in battery charge and discharge process.Therefore the Application and Development of tin carbon composite becomes focus.Mainly containing following several method in the prior art prepares the tin carbon composite and is used for lithium ion battery negative:
Adopt SnO among the Chinese patent application CN101997110A
2Be reflected at air flow protection with carbon and carry out mixed sintering down, contain carbon matrix precursor and carry out sintering and obtain particulate tin carbon negative pole material through sieving to add again.This method coats by secondary carbon, has left enough volumetric expansion spaces to metallic tin, has strengthened the uniformity of electrode interior composition, has improved the stability of serviceability.But the about 420mAh/g of first discharge specific capacity, charge ratio capacity 382mAh/g, the specific capacity of material is not high, and the chemical property of this tin carbon composite remains further to be improved.
(Chemistry of Materials 2005 such as Mijung Noh, 17 (8), 1926-1929.) adopt butter of tin in ethylene glycol, to reduce with tetrahydro boron sodium, obtain the metallic tin particle lithium ion battery negative material that amorphous carbon coat with glucose solution 180 degree water under high pressure thermal responses under argon gas atmosphere again.About the about 200nm of metallic tin particle, the surface has amorphous carbon layer to coat, first discharge specific capacity 789mAh/g, charge ratio capacity 681mAh/g, the irreversible efficient 14% of first charge-discharge, about 664mAh/g after 50 circulations, capability retention 98% has shown excellent chemical property, yet it is expensive to prepare required raw material, the process conditions complexity is not easy to large-scale production.
(Electrochimica Acta 2010,55 (28), 9067-9074.) adopt citric acid and butter of tin sol-gal process to synthesize SnO for Mingxia Gao etc.
2-C composite material precursor, the screening back carbonization under 800 ℃ of conditions of high temperature of process drying and crushing forms, first discharge specific capacity 807mAh/g, charge ratio capacity 545mAh/g, enclosed pasture efficient is 68%, 70 circulation about 380-400mAh/g of specific capacity afterwards first.Therefore the cyclical stability of material awaits further raising.
One kind of Chinese patent application CN101202340A utilize solubility stannate or solubility pink salt and macromolecular compound starch mixture through high temperature to 500-1000 ℃ and be incubated the preparation method of carbonization in 0-10 hour acquisition tin carbon composite, the tin carbon nanometer compound material for lithium ion battery that obtains is at current density 28mA/cm
2, charging and discharging under the voltage 0.01-2V, reversible capacity is 580mAh/g first, and greatly about about 425mAh/g, current density is less after 50 circulations, and the circulation volume under the high current density discharge condition does not have report.
(Advanced Materials (Weinheim such as Gaelle Derrien, Germany) 2007,19 (17), 2336-2340) adopt and the tributyl diphenyl tin to be penetrated in the middle of the hydrosol behind resorcinol and the oxymethylene polymerization method of high temperature reduction to have synthesized the Sn-C composite material of nanostructure.Concrete preparation process be first with resorcinol and formaldehyde at Na
2CO
3Catalysis stir 2h and form the hydrosols for following 70 ℃, spend the night be aged to room temperature after, Na is removed in the ball milling washing
2CO
3The hydrosol is through tert-butyl alcohol immersion filtration, and repeated multiple times is carried out exchange of solvent to the micropore in the hydrosol; The tributyl diphenyl tin and the hydrosol dipping that are dissolved in the tert-butyl alcohol stir a night; Then at 700 ℃, reductase 12 h under the Ar atmosphere promptly obtains the Sn-C composite material of nanostructure.0.8C (about 1Acm
-2g
-1) down reversible specific capacity be 500mAh/g, capacity keeps stable after 200 circulations, the chemical property performance is excellent.Yet synthetic raw material is expensive, and the difficult control of step complexity, condition is unfavorable for large-scale production.
The inventor formerly prepares on the basis of mesoporous carbon invention, carried out with keen determination research, find to use fructose as polymer monomer with carry out the polymerization carbonization of dewatering under pink salt mixes, can synthesize good tin carbon composite, be used for the lithium ion battery negative function admirable, finished the present invention.
Summary of the invention
The objective of the invention is provides a kind of preparation method of easy tin carbon composite in order to overcome the problem that prior art exists, and the tin carbon composite that is used for lithium ion battery negative material of this method preparation further is provided again.
The preparation method of a kind of used as negative electrode of Li-ion battery tin carbon composite of the present invention, be meant and utilizing the mixture by polymer monomer and pink salt to prepare in the method for tin carbon composite through polymerization-processes such as dehydration-carbonization, polymer monomer wherein is a fructose.Polymerization takes place and forms polymer in fructose under slaine and acid condition, the carrying out with polymerization of losing along with moisture, dissolving solubility pink salt wherein crystallization is gradually separated out and is become crystallite and be dispersed in the polymer, through further dehydration carbonization, according to conditions such as carburizing temperatures, pink salt is reduced to nano level metal tin, and part rests on the oxide of tin, be coated in the polymer of carbonization, obtain tin carbon composite of the present invention.
Wherein initial contain fructose soln consist of fructose, pink salt, acid complexing agent and water, as long as wherein water can dissolve pink salt and fructose and be beneficial to poly-be incorporated in dehydration and carbonization in the subsequent handling, hydrolysis for fear of pink salt, add suitable acid and keep certain acidity for well, adding simultaneously can be better with the complexing agent of tin ion complexing, and adding acid complexing agent, to reach this purpose simultaneously better.Add sour the carrying out that also can promote polymerization reaction.General fructose: pink salt: acid complexing agent: water, mol ratio be 1: (0.4～1.6): (0～3): (1～5) is better.The solubility pink salt has multiple commodity optional, stannous chloride for example, and stannic chloride, general stannous chloride is comparatively convenient, and acid complexing agent only needs the sort of acid that can the complexing tin ion to get final product, and for example hydrochloric acid, acetic acid or polyacrylic one or more mixture get final product.
In order to finish the process of polymerization dehydration carbonization, heat described mixture generation polymerization after, continue to improve temperature dehydration and drying and obtain drying composite, carbonization in high temperature solid state reaction obtains the tin carbon composite.The mixture heated polymerizable of preparation, need suitable temperature, can obtain with the method for experiment, general 70～90 ℃ better, be beneficial to polymerization like this and also be convenient to partly dewater along with the evaporation of moisture; Further dehydration, as long as can slough remaining water reposefully so that the subsequent drying operation get final product, general 110～135 ℃ better, prepare for carbonization again, further dryings are better at 170～230 ℃.Therefore for obtained performance tin material with carbon element of the present invention preferably, a kind of polymerization of preferred manufacturing procedure dehydration carbonization may further comprise the steps to be finished: the aforesaid solution that contains fructose and pink salt is heated to 70～90 ℃ and obtains the polymerization dehydrating mixt; Again in 110～135 ℃ of oven dry dehydration in 2 hours; Under inert atmosphere, heated polymerizable dehydrating mixt to 170～230 ℃ are incubated 1～10 hour, are heated to 400～700 ℃ again, are incubated 0～10 hour, put cold then.Carburizing temperature is more preferably at 500～600 ℃, the material that is obtained better performances during as lithium ion battery negative material.During intensification, programming rate is low a bit relatively good, but expends time in, and generally heats up relatively good with 2～5 ℃/min speed.
Concrete preparation contains the solution of fructose and pink salt, can prepare according to aforementioned component, and a kind of preferred step is: dry polyblend is with the fructose solution that is mixed with 0.1～10mol/L soluble in water, is adding the solubility pink salt; Further, obtaining dry polymer can be that polymerization dehydrates in different temperature by preceding method step by step both, progressively improved temperature and operated, and also can continue to stir this solution until the moisture evaporate to dryness, placed 90～150 ℃ of following dryings to make.
The material that method of the present invention is prepared can pass through the crystallization that powder x-ray diffraction (XRD) is tested carbon and carbon, the size of the form of the compound of tin and estimation crystal grain.By electronic scanner microscope (SEM) form of the carbon in high-resolution SEM or transmitted electron flying-spot microscope (TEM) the Direct observation tin carbon composite particularly, the pattern of tin and size, by the BET method can test microvia carbon pore-size distribution.
With the electrochemical properties of the material of the present invention preparation and the character when being assembled into battery, can test with method in common, particularly in the present invention, cyclic voltammetry is to use and is assembled into 2025 button cells in being full of the glove box of argon gas, test the electrochemical properties in its charge and discharge process, the voltage range of using is 0～2V, and sweep speed is 0.1mV/s.Charge-discharge performance is that 2025 button cells that are assembled into test usefulness are tested, charging/discharging voltage scope 0.005～2V, and current density is 100mA/g, uses Wuhan Land CT2001A battery test system to test.
The tap density of tin carbon composite of the present invention is about 1.3g/cm
3Tap density than the graphite-like material with carbon element on the market is bigger, and volume energy density is higher.
A kind of used as negative electrode of Li-ion battery tin carbon composite that also provides preparation in accordance with the present invention to obtain according to the present invention, wherein tin is nano level metal tin and tin-oxide, and carbon is microporous carbon, and it is 1～2nm that the aperture mainly is distributed in.The preparation polymer after through the process that dehydrates last carbonization in, can see from the XRD analysis of the tin carbon composite that obtains, tin exists with tin oxide and/or metallic tin, the XRD that from carburizing temperature is 700 ℃ sample always finds out the characteristic peak that is mainly metallic tin, find out peak and the thin branch of metal that tin oxide is arranged among the XRD of 600 ℃ sample, 500 ℃ sample does not have the peak, can infer that main component is small or unbodied tin oxide, this point from the CV of 500 ℃ the sample figure (accompanying drawing 2) also as can be seen, primary reduction line (from high voltage voltage on earth) differs greatly with later reduction line, therefore the oxidation line too, along with the increase of cycle-index tends towards stability, can be interpreted as that tin oxide has been reduced into metallic tin in reduction process, become the tin lithium alloy.From the TEM figure (accompanying drawing 7) as can be seen, the size of its particle is a nanoscale, be uniformly dispersed, from chemical property, its sample under higher temperature for example 700 ℃ when carrying out carbonization, the composition of tin oxide (XRD peak intensity) is low, performance is relatively poor relatively, the composition of tin oxide when carburizing temperature is 600 ℃ (XRD peak intensity) height, carburizing temperature are low for example 400 ℃ the time, do not have tangible peak, contained tin oxide composition should be also higher, performance is also relatively poor, and when 500～600 ℃ of carburizing temperatures, the composition of metallic tin and tin oxide is moderate in the material of acquisition, on XRD figure, there is not tangible peak to show that its crystal grain is very little or for amorphous state, wherein example best performance when making battery cathode for 500 ℃ is charging and discharging voltage range 0.005-2V, under the 100mA/g current density, prepared composite material reversible specific capacity first can reach 412.7mAh/g, after 40 circulations is 412.5mAh/g, and capability retention is 99.95%, has shown excellent cycle performance.
The present invention has the following advantages with respect to prior art:
1, utilize fructose and pink salt to carry out polymerization and obtain presoma, through the tin carbon composite of dehydration carbonization, raw material is easy to get, and method is simple, and process is easily controlled, and carburizing temperature is lower, saves the energy.
When 2, the tin carbon composite of this method preparation is used for lithium ion battery negative material, specific capacity height, cycle performance excellence.
3, the tin carbon composite of this method preparation is more higher than the graphite-like material with carbon element tap density on the market, and volume energy density is big.
Description of drawings
Fig. 1 is the XRD figure of the described lithium ion battery tin carbon compound cathode materials of embodiment 1-6; The carburizing temperature among the corresponding embodiment of icon representation wherein: 400 ℃ (embodiment 1) expression by embodiment 1 carburizing temperature by 400 ℃ the XRD figure of acquisition material.
Fig. 2 is the CV curve chart of embodiment 2 described lithium ion battery tin carbon compound cathode materials;
Fig. 3 is the battery charging and discharging curve chart of embodiment 2 described lithium ion battery tin carbon compound cathode materials;
Fig. 4 is the battery cyclic curve figure of embodiment 2 described lithium ion battery tin carbon compound cathode materials.
Fig. 5 is the pore distribution curve figure of embodiment 2 described lithium ion battery tin carbon compound cathode materials.
Fig. 6 is embodiment 2 described lithium ion battery tin carbon compound cathode materials absorption/desorption curve charts.
Fig. 7 is the TEM figure of embodiment 5 described lithium ion battery tin carbon compound cathode materials.
Embodiment
Below by specific embodiment the technology that the present invention prepares the method for tin carbon composite is described further.
Embodiment 1
1) with fructose (C
6H
12O
6) and stannous chloride two hydrate (SnCl
2.2H
2O) be initial feed, 13.3g fructose is dissolved in the 20mL water, in solution, add 10.0g SnCl
2.2H
2O, mechanical agitation evenly obtains colourless or faint yellow transparent mixed solution, and heating is warming up to 80 ℃ while stirring, until the moisture evaporate to dryness, at 130 ℃ of oven dry 2h, obtains mixture then;
2) with resulting mixture in the high-purity argon gas atmosphere that flows, be warming up to 200 ℃ and be incubated 2h with 5 ℃/min, be warming up to 400 ℃ with 2 ℃/min again, be cooled to 100 ℃ with 5 ℃ of min, treat that then it naturally cools to room temperature, products therefrom is used as negative electrode of Li-ion battery tin carbon composite.
The binding agent PVDF (PVDF dissolves with 1-Methyl-2-Pyrrolidone) of the conductive agent acetylene black of above-mentioned used as negative electrode of Li-ion battery tin carbon composite and 10wt% and 10wt% mixed make slurry, evenly be coated on the Copper Foil, roll-in after 40 ℃ of oven dry, be washed into diameter 15mm disk, 120 ℃ of vacuum drying 12h, be to electrode with lithium metal then, electrolyte is 1M LiPF
6/ EC+DMC+EMC (volume ratio is 1/1/1), barrier film is Celgard2400, in being full of the glove box of argon gas, be assembled into 2025 button cells, Land CT2001A battery test system carries out charge-discharge test in Wuhan, current density 100mA/g, and the charging/discharging voltage scope is 0.005-2.0V.Electrochemical workstation Im6ex is adopted in CV scan round, sweep speed 0.1mV/s, and voltage range is 0-2V.After tested this tin carbon composite first reversible specific capacity be 394.4mAh/g, 40 times the circulation after be 390.8mAh/g, capability retention is 99.1%.
Embodiment 2
1) with fructose and (SnCl
2.2H
2O) be initial feed, 10.0g fructose is mixed with the solution of 5.56mol/L, in solution, add 10.0g SnCl
2.2H
2O, mechanical agitation evenly obtains colourless or faint yellow transparent mixed solution, and heating is warming up to 80 ℃ while stirring, until the moisture evaporate to dryness, at 130 ℃ of oven dry 2h, obtains mixture then;
2) with resulting mixture in the high-purity argon gas atmosphere that flows, be warming up to 200 ℃ and be incubated 2h with 5 ℃/min, be warming up to 500 ℃ and be incubated 2h with the phase same rate again, be cooled to 100 ℃ with 5 ℃/min again, treat that then it naturally cools to room temperature, products therefrom is used as negative electrode of Li-ion battery tin carbon composite.Its XRD figure as shown in Figure 1, Fig. 7 is its transmission electron microscope photo.
Adopt method identical and condition to the material test that experimentizes with embodiment 1, after tested this tin carbon composite first reversible specific capacity be 364.1mAh/g, 40 times circulate afterwards is 360.9mA/g, capability retention is 99.1%.Fig. 2 is its cyclic voltammetry curve, and Fig. 3-4 is battery charging and discharging curve and capacity cyclic curve.
Embodiment 3
1) with fructose and SnCl
2.2H
2O is an initial feed, and 10.0g fructose is mixed with the solution of 5.56mol/L, adds 10.0g SnCl in solution
2.2H
2O, mechanical agitation evenly obtains colourless or faint yellow transparent mixed solution, and heating is warming up to 90 ℃ while stirring, until the moisture evaporate to dryness, at 130 ℃ of oven dry 2h, obtains mixture then;
2) with resulting mixture in the high-purity argon gas atmosphere that flows, be warming up to 170 ℃ and be incubated 2h with 5 ℃/min, be warming up to 230 ℃ and be incubated 2h with 2 ℃/min again, be warming up to 600 ℃ and be incubated 2h with 2 ℃/min again, be cooled to 100 ℃ with 5 ℃/min again, treat that then it naturally cools to room temperature, products therefrom is used as negative electrode of Li-ion battery tin carbon composite.
Adopt method identical and condition to the material test that experimentizes with embodiment 1, after tested this tin carbon composite first reversible specific capacity be 358.0mAh/g, 40 times circulate afterwards is 128.8mAh/g, capability retention is 36.0%.
Embodiment 4
1) with fructose and SnCl
2.2H
2O is an initial feed, and 10.0g fructose is mixed with the solution of 5.56mol/L, adds 10.0g SnCl in solution
2.2H
2O, mechanical agitation evenly obtains colourless or faint yellow transparent mixed solution, and heating is warming up to 80 ℃ while stirring, until the moisture evaporate to dryness, at 130 ℃ of oven dry 2h, obtains mixture then;
2) with resulting mixture in the high-purity argon gas atmosphere that flows, be warming up to 200 ℃ and be incubated 2h with 5 ℃/min, be warming up to 700 ℃ and be incubated 2h with 2 ℃/min again, be cooled to 100 ℃ with 5 ℃/min again, treat that then it naturally cools to room temperature, products therefrom is used as negative electrode of Li-ion battery tin carbon composite.
Adopt method identical and condition to the material test that experimentizes with embodiment 1, after tested this tin carbon composite first reversible specific capacity be 235.7mAh/g, 40 times circulate afterwards is 148.5mAh/g, capability retention is 63.0%.
Table 1 carburizing temperature and material property contrast table
Embodiment 5
1) with fructose and SnCl
2.2H
2O is an initial feed, and 10.0g fructose is mixed with the solution of 2.78mol/L, adds 12.5g SnCl in solution
2.2H
2O, mechanical agitation evenly obtains colourless or faint yellow transparent mixed solution, and heating is warming up to 75 ℃ while stirring, until the moisture evaporate to dryness, at 130 ℃ of oven dry 2h, obtains mixture then;
2) with resulting mixture in the high-purity argon gas atmosphere that flows, be warming up to 200 ℃ and be incubated 2h with 5 ℃/min, be warming up to 500 ℃ with 2 ℃/min again, be cooled to 100 ℃ with 5 ℃ of min, treat that then it naturally cools to room temperature, products therefrom is used as negative electrode of Li-ion battery tin carbon composite.
Adopt method identical and condition to the material test that experimentizes with embodiment 1, after tested this tin carbon composite first reversible specific capacity be 412.7mAh/g, 40 times circulate afterwards is 412.5mAh/g, capability retention is 99.95%.
Embodiment 6
1) with fructose and SnCl
2.2H
2O is an initial feed, and 10.0g fructose is mixed with the solution of 5.56mol/L, adds 15.0g SnCl in solution
2.2H
2O, mechanical agitation adds the 3.0g polyacrylic acid after evenly waiting to obtain colourless or faint yellow transparent mixed solution again, stirs to make fully in 12 hours to mix, and heating is warming up to 85 ℃ while stirring, until the moisture evaporate to dryness, at 130 ℃ of oven dry 4h, obtains mixture then;
2) resulting mixture is put into the high-purity argon gas atmosphere that tube furnace is flowing, be warming up to 170 ℃ and be incubated 2h with 5 ℃/min, be warming up to 400 ℃ with 2 ℃/min again, be cooled to 100 ℃ with 5 ℃ of min, treat that then it naturally cools to the room temperature products therefrom and is used as negative electrode of Li-ion battery tin carbon composite.
Adopt method identical and condition to the material test that experimentizes with embodiment 1, after tested this tin carbon composite first reversible specific capacity be 571.3mAh/g, 40 times circulate afterwards is 325.8mAh/g, capability retention is 57.0%.
Embodiment 7
1) with fructose and SnCl
2.2H
2O is an initial feed, with 10.0g SnCl
2.2H
2O joins in the hydrochloric acid solution of 0.1mol/L, stirring makes dissolving fully, in solution, add 10.0g fructose again, after mechanical agitation evenly waits to obtain colourless or faint yellow transparent mixed solution, stir to make fully in 3 hours and mix, while stirring heating, be warming up to 90 ℃, until the moisture evaporate to dryness, at 130 ℃ of oven dry 4h, obtain solid mixture then;
2) resulting mixture is put into the high-purity argon gas atmosphere that tube furnace is flowing, be warming up to 200 ℃ and be incubated 2h with 5 ℃/min, be warming up to 500 ℃ with 2 ℃/min again, be cooled to 100 ℃ with 5 ℃ of min, treat that then it naturally cools to the room temperature products therefrom and is used as negative electrode of Li-ion battery tin carbon composite.
Adopt method identical and condition to the material test that experimentizes with embodiment 1, after tested this tin carbon composite first reversible specific capacity be 255.7mAh/g, after 40 circulations is 302.7mAh/g, is 309.3mAh/g after 150 circulations, and capability retention is 121%.
Claims (9)
1. the preparation method of a used as negative electrode of Li-ion battery tin carbon composite, the mixture by polymer monomer and pink salt forms through polymerization dehydration carbonization, it is characterized in that its polymer monomer is a fructose.
2. press the preparation method of a kind of used as negative electrode of Li-ion battery tin carbon composite of claim 1, it is characterized in that the fructose that consists of of mixture: pink salt: acid complexing agent: the mol ratio of water is 1: (0.4～1.6): (0～3): (10～50).
3. by the preparation method of claim 1 or a kind of used as negative electrode of Li-ion battery tin carbon composite of 2, it is characterized in that: described solubility pink salt is a stannous chloride, and acid complexing agent is hydrochloric acid, acetic acid or polyacrylic one or more mixture.
4. press the preparation method of a kind of used as negative electrode of Li-ion battery tin carbon composite of claim 1 to 3, wherein polymerization dehydration carbonization may further comprise the steps and finishes: after heating described mixture generation polymerization, continue to improve temperature dehydration and drying and obtain drying composite, obtain the tin carbon composite in the high temperature solid state reaction carbonization.
5. press the preparation method of a kind of used as negative electrode of Li-ion battery tin carbon composite of claim 4, wherein ℃ carry out polymerization heating described mixture to 75～90, dehydration was carried out 110～135 ℃ of oven dry in 2 hours, drying is under inert atmosphere, heated polymerizable dehydrating mixt to 170～230 ℃ are incubated and carried out in 1～10 hour; Carbonization is at 400～700 ℃, is incubated to carry out in 0～10 hour.
6. by the preparation method of a kind of used as negative electrode of Li-ion battery tin carbon composite of claim 5, wherein carbonization is carried out for tangible 500～550 ℃.
7. according to the preparation method of a kind of used as negative electrode of Li-ion battery tin carbon composite of one of claim 4 to 6, wherein dry polyblend is the solution with the fructose 0.1-8mol/L of being mixed with soluble in water, adding the solubility pink salt, continue agitating solution until the moisture evaporate to dryness, place 90～150 ℃ of following dryings to make.
8. according to the preparation method of a kind of used as negative electrode of Li-ion battery tin carbon composite of claim 7, wherein the solution concentration of the aqueous solution that fructose is mixed with is 2～6mol/L.
9. used as negative electrode of Li-ion battery tin carbon composite is characterized by according to one of claim 1 to 7 method and is prepared from, and wherein tin is nano level metal tin and tin oxide.
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Cited By (8)
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| 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 |
| CN104752069A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method of metallic oxide or metallic oxide composite material |
| CN104868109A (en) * | 2015-05-04 | 2015-08-26 | 南开大学 | Tin oxide and porous carbon composite lithium ion battery anode materials |
| CN105006575A (en) * | 2015-06-23 | 2015-10-28 | 西安博纳材料科技有限公司 | Method for preparing metallic oxide-carbon composite material |
| CN107665972A (en) * | 2017-07-05 | 2018-02-06 | 中国矿业大学 | A kind of Sn@C-material preparation methods of high-performance kalium ion battery negative material |
| CN110078177A (en) * | 2019-04-19 | 2019-08-02 | 广西民族大学 | A kind of SnO2- GAC particle and its preparation method and application |
| CN112510177A (en) * | 2020-11-25 | 2021-03-16 | 华南理工大学 | Sn/C composite negative electrode material for lithium ion battery and preparation method thereof |
| CN115692612A (en) * | 2022-11-03 | 2023-02-03 | 福州大学 | Tin-carbon negative electrode material and preparation method thereof |
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| CN104752069B (en) * | 2013-12-31 | 2018-10-26 | 西北大学 | A kind of preparation method of metal oxide or metal oxide composite |
| CN104868109A (en) * | 2015-05-04 | 2015-08-26 | 南开大学 | Tin oxide and porous carbon composite lithium ion battery anode materials |
| CN104868109B (en) * | 2015-05-04 | 2017-04-19 | 南开大学 | Tin oxide and porous carbon composite lithium ion battery anode materials |
| CN105006575A (en) * | 2015-06-23 | 2015-10-28 | 西安博纳材料科技有限公司 | Method for preparing metallic oxide-carbon composite material |
| CN105006575B (en) * | 2015-06-23 | 2019-06-04 | 西安博纳材料科技有限公司 | A kind of preparation method of metal oxide-carbon composite materials |
| CN107665972A (en) * | 2017-07-05 | 2018-02-06 | 中国矿业大学 | A kind of Sn@C-material preparation methods of high-performance kalium ion battery negative material |
| CN107665972B (en) * | 2017-07-05 | 2020-04-17 | 中国矿业大学 | Preparation method of Sn @ C material of high-performance potassium ion battery negative electrode material |
| CN110078177A (en) * | 2019-04-19 | 2019-08-02 | 广西民族大学 | A kind of SnO2- GAC particle and its preparation method and application |
| CN112510177A (en) * | 2020-11-25 | 2021-03-16 | 华南理工大学 | Sn/C composite negative electrode material for lithium ion battery and preparation method thereof |
| CN115692612A (en) * | 2022-11-03 | 2023-02-03 | 福州大学 | Tin-carbon negative electrode material and preparation method thereof |
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