CN100386906C - Active-carbon-microball coated metal composition negative polar material and preparing method - Google Patents
Active-carbon-microball coated metal composition negative polar material and preparing method Download PDFInfo
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Abstract
The present invention relates to a metal composite coated with active carbon microsphere negative electrode material and a preparation method thereof, which belongs to the technical field of chemical engineering and energy source materials, particularly belongs to the technical field of the preparation of the negative electrode material for lithium secondary batteries. The present invention is characterized in that the material has a structure that metal particles are packaged in hollow carbon microspheres, the metal is a lithium storing active metal with the mass percentage of 30 % to 80 %, resorcin, formaldehyde and metals or metal oxides are adopted as raw materials, and the preparation method comprises reverse micelle emulsion polymerization, high temperature treatment and carbonizing reduction. The negative electrode material put forward in the present invention has the advantages of high initial charge specific capacity, high capacity after a second charge and discharge cycle, fine cycle performance, simple preparation method, low cost and excellent industrial application value.
Description
Technical field
The preparation method of active-carbon-microball coated metal composition negative polar material belongs to Chemical Engineering and energy and material technical field, the particularly preparing technical field of lithium secondary battery cathode material.
Background technology
Lithium ion battery is the novel high-energy secondary cell that twentieth century begins practicability the nineties, have that voltage height, energy density are big, outstanding advantages such as good cycle, self discharge are little, memory-less effect, be widely used in field of portable devices such as mobile phone, notebook computer, digital product, electric tool.Lithium ion battery is as the applications well prospect that electrical source of power showed of electric automobile and hybrid vehicle and in the huge applications potentiality of numerous areas such as military equipment, Aero-Space.
Since eighties of last century lithium ion battery at the beginning of the nineties comes out, with the graphitized carbon material is that negative pole, cobalt acid lithium material are that anodal lithium-ion electric pool technology has obtained huge development, is example with notebook computer with 18650 type batteries, about its specific energy was doubled in 10 years.At present, commercial lithium ion battery still mainly is that negative pole, cobalt acid lithium material are anodal with the graphitized carbon material.Along with developing rapidly of information technology, be the continuous miniaturization of portable set, the intellectuality of representative with mobile phone, notebook computer etc., require its power supply high-energy-densityization more.In addition, field such as electric automobile requires motive-power battery must have higher energy density, lower cost and better fail safe.The performance of commodity lithium ion battery more and more can not satisfy the requirement of above-mentioned development, and wherein negative material is one of important restraining factors.
The subject matter that graphite cathode material exists is: (1) electrographite needs to make through the high temperature graphitization processing at 1900 ℃～2800 ℃, and temperature is too high; (2) theoretical specific capacity is 372mAh/g, and is lower; (3) weak structure can cause very limited stability, and is also extremely sensitive to electrolyte.For overcoming these shortcomings, people are devoted to research and develop new negative material always when graphite material is constantly carried out modification.At present, the negative material of lithium ion battery also has amorphous carbon material, silica-base material, tin-based material, other negative material such as novel alloy except that graphite material.The reversible capacity of wherein non-carbon class material is more much higher than the classical capacity 372mAh/g of graphite, can form Li such as the Li-Sn binary system
4.4The alloy of Sn, theoretical capacity is up to 994mAh/g.But this metalloid alloy negative material change in volume in the removal lithium embedded process is very big, and its structural stability is very poor, thereby causes alloy pulverization to lose efficacy, and cycle performance is relatively poor.In recent years, people by with metal and other materials particularly material with carbon element carry out compoundly, obtained the composite material of capacity height, good cycle.This has benefited from the high power capacity of alloy material on the one hand, also has benefited from stability of structure in the material with carbon element cyclic process on the other hand.(Chem.Mater.2002 such as H.Li for example, 14:103) prepared the SnSb/HCS composite material, wherein HCS is that diameter is the nano-pore carbosphere of 5-20 μ m, in the ball is but the undefined structure of graphite linings composition, and the aperture that wherein distributing is the nano-pore of 0.5-3nm.With HCS is skeleton, with nanometer SnSb alloying pellet equably pinning in its surface, the rare fusion of Nanoalloy particle is reunited in charge and discharge process like this, thereby has excellent cycle performance, the reversible capacity of 35 circulations is stabilized in about 500mAh/g.
The method of reported in literature need just can obtain better electrochemical performance with the alloying pellet nanometer at present, generally all is to belong to halogen by reducing agent reductive water GOLD FROM PLATING SOLUTION to obtain Nanoalloy.But this class methods practicality is got up cost of material than higher, the complicated difficult control of preparation process, and the Cl in the product
-, OH
-Be difficult to Ex-all Deng impurity.
Summary of the invention
The composite structure of the present invention's design is that metallic particles is packaged in the carbosphere of hollow, and the advantage of this structure is: the carbon ball energy effective isolation metallic particles of hollow, in the electrochemistry circulation, avoid reuniting; The zone of hollow can hold the change in volume in the metal alloy removal lithium embedded process; In addition, carbosphere itself also is a storage lithium active material, and extra lithium storage content can be provided.
The present invention is a raw material with resorcinol, formaldehyde, metal or metal oxide, method by reverse micelle emulsion polymerisation and high-temperature process carbonizing reduction has prepared active-carbon-microball coated metal composition negative polar material, provides a kind of method simply direct, with low cost for preparing spherical nanocarbon/metal compound.
The active-carbon-microball coated metal composition negative polar material that the present invention proposes is characterised in that described metal is a storage lithium reactive metal, and described storage lithium reactive metal is covered by in the active-carbon-microball, and its mass percent is 30%～80%.
Described storage lithium reactive metal is a kind of among Sn, Sn/Sb alloy, Sn/Cu alloy or the Si.
The preparation method of active-carbon-microball coated metal composition negative polar material is characterized in that, it contains following steps successively:
(1) oxide particle that will store up lithium reactive metal or storage lithium reactive metal is worn into fine powder;
(2) resorcinol, formaldehyde are dissolved in the deionized water, add base catalyst, add the fine powder that step (1) obtains then, stir, obtain mixed solution; Wherein the mol ratio of resorcinol and formaldehyde is 1: 1～3: 1, and the mol ratio of base catalyst and resorcinol is 0.005: 1～0.03: 1, and the fine powder of interpolation and the mass ratio of resorcinol are 0.2: 1～1: 1;
(3) above-mentioned mixed solution is joined in the oil phase, add surfactant and form the reverse micelle emulsion, wherein the quality of surfactant is 1%～15% of an oil phase, the volume ratio of mixed solution and oil phase is 0.02: 1～0.1: 1, the reverse micelle emulsion that obtains is under 20 ℃～80 ℃ temperature, under the rotating speed of 200rpm～1200rpm stirs, obtain the phenolic resin gel microspheres with solid;
(4) change step (3) gained phenolic resin gel microspheres with solid material over to solid separator and carry out Separation of Solid and Liquid, isolated solid moves to the vacuum drying oven drying, removes the oil phase substance of phenolic resin gel microspheres with solid surface attachment;
(5) step (4) products therefrom is placed in the reactor, under inert gas shielding, be warming up to 800 ℃～1200 ℃, isothermal reaction, order so cools off in reactor, obtains the spherical cathode composite materials of active-carbon-microball coated metal.
Described storage lithium reactive metal is Si.The oxide of described storage lithium reactive metal is SnO
2, SnO
2And Sb
2O
3Mixture, SnO
2A kind of with in the mixture of CuO.
Described base catalyst is NaOH or Na
2CO
3
Described surfactant is a kind of among SPAN80, polysorbate60, the TritonX X-200.
Described oil phase is a kind of in kerosene, cyclohexylamine or the cyclohexane.
The negative material that evidence, the present invention propose has capacity and excellent cycle performance after the higher initial charge specific capacity time charge and discharge cycles, and its preparation method is simple, and is with low cost, and good industrial application value is arranged.
Description of drawings
Fig. 1 is the SEM pattern of active-carbon-microball coated metal composition tin.
Embodiment
The invention provides a kind of method of lithium secondary battery anode active-carbon-microball coated metal tin composite material, its concrete implementation step is as follows:
(1) a certain amount of metal or metal oxide powder are placed stainless steel ball mill container, built-in stainless steel abrading-ball behind the ball milling certain hour, obtains the powder particle (general particle diameter is less than 1 μ m) of refinement.
(2) resorcinol, formaldehyde are dissolved in according to certain mol proportion and obtain settled solution in the deionized water, add base catalyst, add the fine powder that step (1) obtains then, stir, and obtain mixed solution.Wherein the mol ratio of resorcinol and formaldehyde is 1: 1～3: 1, and the mol ratio of base catalyst and resorcinol is 0.005: 1～0.03: 1, and the fine powder granules of adding and the mass ratio of resorcinol are 0.2: 1～1: 1;
(3) above-mentioned mixed solution is joined in the oil phase, add surfactant and form the reverse micelle emulsion, wherein the surfactant quality is 1%～15% of an oil phase, and the volume ratio of mixed solution and oil phase is (0.02～0.1): 1.The reverse micelle emulsion that obtains keeps 20 ℃～80 ℃ temperature to carry out the polymerization reaction time enough under the rotating speed of 200rpm～1200rpm stirs, and obtains the phenolic resin gel microspheres with solid.
(4) change step (3) gained material over to solid separator and carry out Separation of Solid and Liquid, isolated solid moves to the vacuum drying oven drying, removes the oil phase substance of microspheres with solid surface attachment.
(5) step (4) products therefrom is placed reactor, under nitrogen or other inert gas shielding, be warming up to 800 ℃～1200 ℃, isothermal reaction, natural cooling in reactor obtains the spherical composite materials of active-carbon-microball coated metal.
Introduce embodiments of the invention below:
Example 1
The 5.5g resorcinol is dissolved in the 5mL formalin (37%), adds the settled solution that deionized water is configured to 20mL then, add 0.0275g anhydrous Na OH, add SnO behind the 1g ball milling then as catalyst
2Powder stirs.Then this solution is scattered in the kerosene that 200mL is dissolved with 12g SPAN80, forms the reverse micelle emulsion.Under 20 ℃, rotating speed is after phenolic aldehyde polymerization reaction 24h is carried out in the 200rpm stirring, to obtain the phenol formaldehyde condensate glueballs.The microspheres with solid that obtains is gone out the kerosene of surface adhesion in 200 ℃ of vacuum.In tubular react furnace, under the nitrogen atmosphere protection, be warming up to 800 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of active-carbon-microball coated metal tin at last.Recording this product average grain diameter is 60～80 μ m, sees Fig. 1.Metallic tin content is 30.2% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this active-carbon-microball coated metal tin composite material initial charge specific capacity at room temperature is 455mAh/g, and capability retention is 83.2% after 50 charge and discharge cycles.
Example 2
The 5.5g resorcinol is dissolved in the 10mL formalin (37%), adds the settled solution that deionized water is configured to 20mL then, add the 0.05g anhydrous Na
2CO
3As catalyst, add SnO behind the 2g ball milling then
2Powder stirs.Then this solution is scattered in the kerosene that 400mL is dissolved with 15g SPAN80, forms the reverse micelle emulsion.Under 30 ℃, rotating speed is after phenolic aldehyde polymerization reaction 24h is carried out in the 600rpm stirring, to obtain the phenol formaldehyde condensate glueballs.The microspheres with solid that obtains is gone out the kerosene of surface adhesion in 200 ℃ of vacuum.In tubular react furnace, under the nitrogen atmosphere protection, be warming up to 900 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of active-carbon-microball coated metal tin at last.Recording this product average grain diameter is 20～30 μ m, and metallic tin content is 61.3% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this active-carbon-microball coated metal tin composite material initial charge specific capacity at room temperature is 548mAh/g, and capability retention is 81.1% after 50 charge and discharge cycles.
Example 3
The 5.5g resorcinol is dissolved in the 15mL formalin (37%), adds the settled solution that deionized water is configured to 20mL then, add 0.165g anhydrous Na CO
3As catalyst, add SnO behind the 5g ball milling then
2Powder stirs.Then this solution is scattered in the cyclohexylamine that 1000mL is dissolved with 10g SPAN80, forms the reverse micelle emulsion.Under 80 ℃, rotating speed is after phenolic aldehyde polymerization reaction 3h is carried out in the 1200rpm stirring, to obtain the phenol formaldehyde condensate glueballs.The microspheres with solid that obtains is gone out the cyclohexylamine of surface adhesion in 200 ℃ of vacuum.In tubular react furnace, under the nitrogen atmosphere protection, be warming up to 1200 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of active-carbon-microball coated metal tin at last.Recording this product average grain diameter is 40～50 μ m, and metallic tin content is 79.6% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this active-carbon-microball coated metal tin composite material initial charge specific capacity at room temperature is 784mAh/g, and capability retention is 56.3% after 50 charge and discharge cycles.
Example 4
The 5.5g resorcinol is dissolved in the 15mL formalin (37%), adds the settled solution that deionized water is configured to 20mL then, add 0.1g anhydrous Na CO
3As catalyst, add SnO behind the 1g ball milling then
2/ Sb
2O
3Mixed oxide powder (present embodiment adopted mol ratio 2: 1, and Sn, Sb are storage lithium metals, and the alloy of the two mol ratio formation arbitrarily all is available lithium ion battery negative material) stirs.Then this solution is scattered in the cyclohexane that 600mL is dissolved with 15g TritonX X-200, forms the reverse micelle emulsion.Under 60 ℃, rotating speed is after phenolic aldehyde polymerization reaction 6h is carried out in the 400rpm stirring, to obtain the phenol formaldehyde condensate glueballs.The microspheres with solid that obtains is gone out the cyclohexane of surface adhesion in 200 ℃ of vacuum.In tubular react furnace, under the nitrogen atmosphere protection, be warming up to 1000 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of active-carbon-microball coated metal tin pewter at last.Recording this product average grain diameter is 20～30 μ m, and tin pewter content is 35.7% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this active-carbon-microball coating tin pewter composite materials initial charge specific capacity at room temperature is 406mAh/g, and capability retention is 89.6% after 50 charge and discharge cycles.
Example 5
The 5.5g resorcinol is dissolved in the 10mL formalin (37%), adds the settled solution that deionized water is configured to 20mL then, add 0.0275g anhydrous Na OH, add SnO behind the 3g ball milling then as catalyst
2/ Sb
2O
3Mixed oxide powder (present embodiment adopted mol ratio 4: 1, and Sn, Sb are storage lithium metals, and the alloy of the two mol ratio formation arbitrarily all is available lithium ion battery negative material) stirs.Then this solution is scattered in the cyclohexylamine that 600mL is dissolved with the 15g polysorbate60, forms the reverse micelle emulsion.Under 60 ℃, rotating speed is after phenolic aldehyde polymerization reaction 6h is carried out in the 600rpm stirring, to obtain the phenol formaldehyde condensate glueballs.The microspheres with solid that obtains is gone out the cyclohexane of surface adhesion in 200 ℃ of vacuum.In tubular react furnace, under the nitrogen atmosphere protection, be warming up to 1000 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of active-carbon-microball coated metal tin pewter at last.Recording this product average grain diameter is 20～30 μ m, and tin pewter content is 58.1% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this active-carbon-microball coating tin pewter composite materials initial charge specific capacity at room temperature is 558mAh/g, and capability retention is 85.4% after 50 charge and discharge cycles.
Example 6
The 5.5g resorcinol is dissolved in the 10mL formalin (37%), adds the settled solution that deionized water is configured to 20mL then, add the 0.05g anhydrous Na
2CO
3(C), add SnO behind the 3g ball milling then as catalyst
2/ CuO mixed oxide powder, wherein CuO and SnO
2Mol ratio be that (mixed oxide powder was for gun-metal, Sn in 6: 5
5Cu
6Be best negative material, and the gun-metal performance of other ratio is all relatively poor), stir.Then this solution is scattered in the kerosene that 800mL is dissolved with 10g SPAN80, forms the reverse micelle emulsion.Under 40 ℃, rotating speed is after phenolic aldehyde polymerization reaction 6h is carried out in the 800rpm stirring, to obtain the phenol formaldehyde condensate glueballs.The microspheres with solid that obtains is gone out the kerosene of surface adhesion in 200 ℃ of vacuum.In tubular react furnace, under the nitrogen atmosphere protection, be warming up to 900 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of active-carbon-microball coated metal gun-metal at last.Recording this product average grain diameter is 30～40 μ m, and signal bronze content is 52.6% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this active-carbon-microball coated metal gun-metal composite materials initial charge specific capacity at room temperature is 342mAh/g, and capability retention is 90.6% after 50 charge and discharge cycles.
Example 7
The 5.5g resorcinol is dissolved in the 10mL formalin (37%), adds the settled solution that deionized water is configured to 20mL then, add 0.05g anhydrous Na CO
3As catalyst, add the silica flour behind the 2g ball milling then, stir.Then this solution is scattered in the kerosene that 600mL is dissolved with 10g SPAN80, forms the reverse micelle emulsion.Under 25 ℃, rotating speed is after phenolic aldehyde polymerization reaction 24h is carried out in the 600rpm stirring, to obtain the phenol formaldehyde condensate glueballs.The microspheres with solid that obtains is gone out the kerosene of surface adhesion in 200 ℃ of vacuum.In tubular react furnace, under the nitrogen atmosphere protection, be warming up to 1000 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of active-carbon-microball coated metal silicon at last.Recording this product average grain diameter is 20～30 μ m, and silicone content is 50.9% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this active-carbon-microball coated metal silicon compound material initial charge specific capacity at room temperature is 993mAh/g, and capability retention is 76.5% after 50 charge and discharge cycles.
Claims (6)
1. the preparation method of active-carbon-microball coated metal composition negative polar material is characterized in that, it contains following steps successively:
(1) oxide particle that will store up lithium reactive metal or storage lithium reactive metal is worn into fine powder;
(2) resorcinol, formaldehyde are dissolved in the deionized water, add base catalyst, add the fine powder that step (1) obtains then, stir, obtain mixed solution; Wherein the mol ratio of resorcinol and formaldehyde is 1: 1～3: 1, and the mol ratio of base catalyst and resorcinol is 0.005: 1～0.03: 1, and the fine powder of interpolation and the mass ratio of resorcinol are 0.2: 1～1: 1;
(3) above-mentioned mixed solution is joined in the oil phase, add surfactant and form the reverse micelle emulsion, wherein the quality of surfactant is 1%～15% of an oil phase, the volume ratio of mixed solution and oil phase is 0.02: 1～0.1: 1, the reverse micelle emulsion that obtains is under 20 ℃～80 ℃ temperature, under the rotating speed of 200rpm～1200rpm stirs, obtain the phenolic resin gel microspheres with solid;
(4) change step (3) gained phenolic resin gel microspheres with solid material over to solid separator and carry out Separation of Solid and Liquid, isolated solid moves to the vacuum drying oven drying, removes the oil phase substance of phenolic resin gel microspheres with solid surface attachment;
(5) step (4) products therefrom is placed in the reactor, under inert gas shielding, be warming up to 800 ℃～1200 ℃, isothermal reaction, natural cooling in reactor obtains the spherical cathode composite materials of active-carbon-microball coated metal.
2. the preparation method of active-carbon-microball coated metal composition negative polar material as claimed in claim 1 is characterized in that, described storage lithium reactive metal is Si.
3. the preparation method of active-carbon-microball coated metal composition negative polar material as claimed in claim 1 is characterized in that, the oxide of described storage lithium reactive metal is SnO
2, SnO
2And Sb
2O
3Mixture, SnO
2A kind of with in the mixture of CuO.
4. the preparation method of active-carbon-microball coated metal composition negative polar material as claimed in claim 1 is characterized in that, described base catalyst is NaOH or Na
2CO
3
5. the preparation method of active-carbon-microball coated metal composition negative polar material as claimed in claim 1 is characterized in that, described surfactant is a kind of among SPAN80, polysorbate60, the TritonX X-200.
6. the preparation method of active-carbon-microball coated metal composition negative polar material as claimed in claim 1 is characterized in that, described oil phase is a kind of in kerosene, cyclohexylamine or the cyclohexane.
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| CN102054974B (en) * | 2010-12-07 | 2012-11-21 | 浙江大学 | Preparation method for stannic oxide/carbon composite hollow balls |
| CN103545523A (en) * | 2013-10-30 | 2014-01-29 | 北京化工大学 | Porous carbon microsphere, preparation method and lithium ion battery negative electrode material |
| US10511017B2 (en) * | 2015-05-27 | 2019-12-17 | The George Washington University | Hollow carbon nanosphere composite based secondary cell electrodes |
| CN105742611B (en) * | 2016-05-06 | 2018-09-21 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium ion battery negative material, preparation method and lithium ion battery |
| CN106654230A (en) * | 2017-01-21 | 2017-05-10 | 深圳市朗能动力技术有限公司 | Method for preparing silicon-carbon negative electrode material employing suspended emulsion polymerization method |
| CN106784759A (en) * | 2017-04-01 | 2017-05-31 | 重庆大学 | A kind of silicon/activated carbon composite negative pole material and preparation method thereof |
| CN108376774B (en) * | 2018-02-08 | 2021-08-24 | 江西省科学院应用物理研究所 | Tin-carbon composite hollow sphere material for negative electrode of sodium ion battery and application of tin-carbon composite hollow sphere material |
| CN108336337B (en) * | 2018-02-08 | 2021-08-17 | 魏阅文 | Sodium ion battery negative electrode material C/Sb2O3Preparation and application of/C composite hollow sphere material |
| CN108788181B (en) * | 2018-07-10 | 2021-07-06 | 哈尔滨理工大学 | Method for synthesizing core-shell structure carbon-coated gold nanoparticles with regular spherical morphology |
| CN110838574A (en) * | 2018-08-16 | 2020-02-25 | 深圳市贝特瑞新能源材料股份有限公司 | High-capacity composite negative electrode material for lithium ion battery, preparation method of high-capacity composite negative electrode material and lithium ion battery comprising composite material |
| CN109686944B (en) * | 2018-12-21 | 2022-05-31 | 四川翔丰华新能源材料有限公司 | Carbon-coated lithium alloy composite electrode material and preparation method thereof |
| CN110842192B (en) * | 2019-11-13 | 2020-08-25 | 四川大学 | Nitrogen-doped porous carbon-coated hydrogen storage alloy powder and preparation method thereof |
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