CN102299302A - Hydrothermal preparation method of tin-cobalt alloy cathode material for lithium ion battery - Google Patents
Hydrothermal preparation method of tin-cobalt alloy cathode material for lithium ion battery Download PDFInfo
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- CN102299302A CN102299302A CN2011101967564A CN201110196756A CN102299302A CN 102299302 A CN102299302 A CN 102299302A CN 2011101967564 A CN2011101967564 A CN 2011101967564A CN 201110196756 A CN201110196756 A CN 201110196756A CN 102299302 A CN102299302 A CN 102299302A
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- cobalt alloy
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Abstract
The invention relates to a hydrothermal preparation method of a tin-cobalt alloy cathode material for a lithium ion battery, which belongs to the technical field of chemical electrode material manufacture technology. The method comprises the following steps: dissolving dehydrate tin dichloride and hexahydrate cobaltous dichloride in deionized water; adding sodium borohydride into deionized water, stirring for fully dissolving, then mixing two solutions; transferring a prepared mixture to a sealed reaction vessel, taking the reaction vessel out after finishing the reaction and cooling to the room temperature, pump filtrating a suspension containing black deposition, washing, drying to obtain the tin-cobalt alloy cathode material. The invention has the advantages of simple operation, easy process control, low energy consumption, environmental protection and no secondary pollution generation, so that the tin-cobalt alloy cathode material which takes Co3Sn2 as a main phase is obtained, and the tin-cobalt alloy cathode material has high initial charge and discharge specific capacity and good cycle performance when being as the cathode material of the lithium ion battery.
Description
Technical field
The present invention relates to a kind of hydrothermal preparing process of tin-cobalt alloy negative pole material of lithium-ion battery, belong to chemical industry electrode material manufacturing process technology field.
Background technology
21 century, energy shortage is becoming the bottleneck of restriction human social development day by day, and world oil can also be exploited and use about 30 years, and the colliery reserves also allow of no optimist, and the world energy sources crisis of the last century six the seventies outburst has been beaten alarm bell to people especially.And, along with the deterioration of environment for human survival, the environmental protection energy that the searching that people are eager is new, and improve existing rate of energy.Research the carrying out also like a raging fire of solar energy, wind energy, tidal energy, biological energy source, nuclear energy, geothermal energy, Hydrogen Energy equal energy source.In the energy that all have developed, electric energy is undoubtedly a kind of energy of most convenient cleaning, and therefore, having environmental protection characteristic and having high-octane chemical power source has become the research focus.Lithium ion battery will become following development trend as typical case's representative of novel high-energy battery.
One of key problem in technology of lithium ion battery is negative pole, and its R﹠D work is in very active state always.Wherein, exploitation has more that the negative material of height ratio capacity, good electrical chemical property is the important topic of Study on Li-ion batteries using.At present, it is the carbon materials of representative that the lithium ion battery negative material of having realized commercial applications is confined to graphite, and its theoretical maximum specific capacity only has 372mAh/g, can not satisfy the requirement of high specific energy battery applications.Tin base cathode material is at Li
+Embed with the reversible reaction of deviating from form LixSn (x=[4.4]).In theory, 1 tin atom can form alloys with 4.4 lithium atoms, so tin has bigger lithium storage content, is about 990mAh/g, and this has tin-based material becomes the great potential of widely used lithium ion battery negative material.Simple substance tin is during as lithium ion battery negative material, Li
+Embed and deviate from that its volume change is up to 100%～300% in the process, electrode easily breaks and pulverizing, so simple substance tin should not directly be used as lithium ion battery negative material.Research to tin-based material at present mainly concentrates on tin-based oxide, kamash alloy and these several respects of tinbase compound.
Tin-cobalt alloy negative electrode material (comprises CoSn, CoSn
2, CoSn
3, Co
3Sn
2Deng) be Recent study one of the most a kind of tin base alloy anode material, as lithium ion battery negative material, this material has the high theoretical lithium storage content, has a good application prospect as lithium ion battery negative material.Studies show that in the past, the chemical property of tin-cobalt alloy negative electrode material mainly are subjected to factor affecting such as Sn/Co ratio, active material crystal habit, particle size and electrode structure.In the present invention, we study tin-cobalt alloy negative electrode material, have optimized preparation and treatment process, and having obtained principal phase is Co
3Sn
2Tin-cobalt alloy negative electrode material, shown higher first charge-discharge specific capacity and excellent cycle performance when the lithium ion battery negative material.This synthetic method has the value of further research and popularization.
Summary of the invention
The objective of the invention is to have in order to solve the prior art for preparing tin-cobalt alloy negative electrode material that method complexity, energy consumption are higher, easily produce the problem of secondary pollution in the building-up process, a kind of hydrothermal preparing process of tin-cobalt alloy negative pole material of lithium-ion battery is provided, this method is simple, process is controlled easily, has shown excellent electrochemical properties during as lithium ion battery negative material.
The objective of the invention is to be achieved through the following technical solutions.
The hydrothermal preparing process of a kind of tin-cobalt alloy negative pole material of lithium-ion battery of the present invention, concrete steps are:
1) two hydration stannous chloride and six hydration cobaltous dichlorides are dissolved in deionized water in molar ratio at 1～5: 1, wherein dissolving back Sn
2+Concentration be 0.02～5.0mol/L, Co
2+Concentration be 0.02～1.0mol/L;
2) sodium borohydride is joined in the deionized water, stirring is dissolved it fully, obtains the aqueous solution of sodium borohydride, and the concentration of dissolving back sodium borohydride is 0.01～2.5mol/L;
3) with step 2) sodium borohydride aqueous solution of preparation joins in the solution of step 1) preparation, stirs it is mixed;
4) mixed solution with the step 3) preparation is transferred in the closed reactor, and reaction temperature is 120～220 ℃, and the reaction time is 12～60h;
5) after reaction is finished, reactor is taken out and be cooled to room temperature, the muddy liquid that will contain black precipitate carries out suction filtration, washing, oven dry, promptly obtains tin-cobalt alloy negative electrode material.
Above-mentioned steps 3) amount of substance of sodium borohydride is 6～18: 1 with the ratio of the amount of substance of stannous chloride in.
Beneficial effect
Preparation technology of the present invention is simple to operate, and process is controlled easily, and energy consumption is lower, and is environmentally friendly, do not produce secondary pollution, and having obtained principal phase is Co
3Sn
2Tin-cobalt alloy negative electrode material, shown higher first charge-discharge specific capacity and excellent cycle performance when the lithium ion battery negative material.
Description of drawings
Fig. 1 is the XRD figure spectrum of the tin-cobalt alloy negative electrode material of embodiment 1 preparation;
Specific capacity and enclosed pasture efficiency curves figure when the tin-cobalt alloy negative electrode material that Fig. 2 prepares for embodiment 1 discharges and recharges under 100mA/g.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is elaborated.
Embodiment
A kind of preparation method of tin-cobalt alloy negative pole material of lithium-ion battery, concrete preparation process is as follows:
1) the two hydration stannous chloride of 4.060g and the six hydration cobaltous dichlorides of 1.428g are joined in the deionized water of 50ml, stirring is dissolved it fully;
2) sodium borohydride with 2.724g joins in the deionized water of 35ml, stirs it is dissolved fully;
3) with step 2) aqueous solution of sodium borohydride of preparation splashes in the solution of step 1) preparation, stirs it is mixed;
4) mixed solution with the step 3) preparation is transferred in the closed reactor, and reaction temperature is 160 ℃, and the reaction time is 24h;
5) after reaction is finished, reactor is taken out and be cooled to room temperature, the muddy liquid that will contain black precipitate carries out suction filtration, washing, oven dry, promptly obtains tin-cobalt alloy negative electrode material.
To obtain tin-cobalt alloy negative electrode material is applied to carry out charging and discharging capacity and cycle performance test behind the lithium ion battery negative material: tin-cobalt alloy negative electrode material and conductive agent gas-phase growth of carbon fibre (VGCF), 80%: 10%: 10% by mass percentage mixed of binding agent Kynoar (PVDF) are made electrode slice as work electrode, lithium metal is to electrode, the LiF of 1mol/L
6/ EC-DMC (volume ratio 1: 1) is an electrolyte, is assembled into simulated battery in the argon gas atmosphere glove box.Simulated battery is carried out charge-discharge test, and voltage range is 0.01～2.0V (vs.Li
+/ Li), current density is 100mA/g.
Test result: the XRD figure spectrum of prepared tin-cobalt alloy negative electrode material is composed as can be seen by XRD figure as shown in Figure 1, and prepared tin-cobalt alloy negative electrode material principal phase is Co
3Sn
2, also have CoSn simultaneously
2Phase, impurity are SnO, and the research of follow-up further improvement synthetic method is carried out, to remove the influence of impurity.Specific capacity and enclosed pasture efficiency curves are as shown in Figure 2 when discharging and recharging, its discharge first (embedding lithium) specific capacity and charging (taking off lithium) specific capacity are respectively 916.4mAh/g, 678.8mAh/g, 20 week of circulation back its discharge (embedding lithium) specific capacities and charging (taking off lithium) specific capacity be respectively 410.1mAh/g, 378.9mAh/g.
Claims (6)
1. the hydrothermal preparing process of a tin-cobalt alloy negative pole material of lithium-ion battery is characterized in that concrete steps are:
1) two hydration stannous chloride and six hydration cobaltous dichlorides are dissolved in deionized water in molar ratio at 1～5: 1;
2) sodium borohydride is joined in the deionized water, stirring is dissolved it fully, obtains the aqueous solution of sodium borohydride;
3) with step 2) sodium borohydride aqueous solution of preparation joins in the solution of step 1) preparation, stirs it is mixed;
4) mixed solution with the step 3) preparation is transferred in the closed reactor;
5) after reaction is finished, reactor is taken out and be cooled to room temperature, the muddy liquid that will contain black precipitate carries out suction filtration, washing, oven dry, promptly obtains tin-cobalt alloy negative electrode material, and the tin-cobalt alloy negative electrode material that obtains is that principal phase is Co
3Sn
2Tin-cobalt alloy negative electrode material, shown the cycle performance that high first charge-discharge specific capacity is become reconciled when the lithium ion battery negative material.
2. the hydrothermal preparing process of a kind of tin-cobalt alloy negative pole material of lithium-ion battery according to claim 1 is characterized in that: Sn after two hydration stannous chloride are dissolved in the deionized water in the step 1)
2+Concentration be 0.02～5.0mol/L.
3. the hydrothermal preparing process of a kind of tin-cobalt alloy negative pole material of lithium-ion battery according to claim 1 is characterized in that: Co after six hydration cobaltous dichlorides are dissolved in the deionized water in the step 1)
2+Concentration be 0.02～1.0mol/L.
4. the hydrothermal preparing process of a kind of tin-cobalt alloy negative pole material of lithium-ion battery according to claim 1, it is characterized in that: the amount of substance of sodium borohydride is 6～18: 1 with the ratio of the amount of substance of stannous chloride in the step 3).
5. the hydrothermal preparing process of a kind of tin-cobalt alloy negative pole material of lithium-ion battery according to claim 1 is characterized in that: step 2) in the concentration of sodium borohydride be 0.01～2.5mol/L.
6. the hydrothermal preparing process of a kind of tin-cobalt alloy negative pole material of lithium-ion battery according to claim 1, it is characterized in that: reaction temperature is 120～220 ℃ in the step 4), the reaction time is 12～60h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103236526A (en) * | 2013-04-10 | 2013-08-07 | 太原理工大学 | Lithium ion battery negative electrode material hollow tin alloy nanoparticles and preparation method thereof |
| CN111029570A (en) * | 2019-11-27 | 2020-04-17 | 长沙理工大学 | Cobalt borate/graphene composite material for lithium ion battery cathode and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102034960A (en) * | 2009-09-25 | 2011-04-27 | 比亚迪股份有限公司 | Tin-based anode material and preparation method thereof as well as battery |
-
2011
- 2011-07-14 CN CN2011101967564A patent/CN102299302A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102034960A (en) * | 2009-09-25 | 2011-04-27 | 比亚迪股份有限公司 | Tin-based anode material and preparation method thereof as well as battery |
Non-Patent Citations (2)
| Title |
|---|
| JIANCHAO HE, ET AL.: "Hydrothermal synthesis and electrochemical properties of nano-sized Co-Sn alloy anodes for lithium ion batteries", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 508, 9 September 2010 (2010-09-09) * |
| 谢健，赵新兵等: "纳米Co-Sn金属间化合物的合成、表征及电化学吸放锂行为", 《物理化学学报》, vol. 22, no. 11, 30 November 2006 (2006-11-30) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103236526A (en) * | 2013-04-10 | 2013-08-07 | 太原理工大学 | Lithium ion battery negative electrode material hollow tin alloy nanoparticles and preparation method thereof |
| CN111029570A (en) * | 2019-11-27 | 2020-04-17 | 长沙理工大学 | Cobalt borate/graphene composite material for lithium ion battery cathode and preparation method thereof |
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