CN1877886A - Metal particle-cladded active carbon microsphere cathode composite materials and method for preparing same - Google Patents
Metal particle-cladded active carbon microsphere cathode composite materials and method for preparing same Download PDFInfo
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- CN1877886A CN1877886A CNA2006100120066A CN200610012006A CN1877886A CN 1877886 A CN1877886 A CN 1877886A CN A2006100120066 A CNA2006100120066 A CN A2006100120066A CN 200610012006 A CN200610012006 A CN 200610012006A CN 1877886 A CN1877886 A CN 1877886A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000004005 microsphere Substances 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 title abstract description 10
- 239000005011 phenolic resin Substances 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 17
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 16
- 230000002441 reversible effect Effects 0.000 claims description 16
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000693 micelle Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 claims description 4
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 claims description 4
- 229940113124 polysorbate 60 Drugs 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910001245 Sb alloy Inorganic materials 0.000 claims description 2
- 239000011806 microball Substances 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 239000010406 cathode material Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 238000006263 metalation reaction Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 16
- 229910052718 tin Inorganic materials 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000011946 reduction process Methods 0.000 description 7
- 229910000498 pewter Inorganic materials 0.000 description 6
- 239000010957 pewter Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 239000011805 ball Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910006913 SnSb Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- -1 lithium metals Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an active carbon micro-sphere-packing metal compound cathode material and making method in the chemical engineering and source material technological domain, which is characterized by the following: blending metal grain in the active carbon micro-sphere; making the metal as Li-reserving active metal at 30-80 percent; adopting phenol resin, metal or oxidation as priority; proceeding high-temperature disposal to carbonation reduction through solidifying inversed-colloidal group emulsion. The invention possesses higher first charging specific capacity and second charging and discharging circulated capacitance, which displays excellent circulating property.
Description
Technical field
Metal particle-cladded active carbon microsphere cathode composite materials and preparation method thereof belongs to Chemical Engineering and energy and material technical field, particularly the technical field of preparation 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.For example (Chem.Mater.2002 14:103) has prepared the SnSb/HCS composite material, and wherein HCS is that diameter is the nano-pore carbosphere of 5-20 μ m, is the undefined structure that graphite linings is formed in the ball, and the aperture that wherein distributing is the nano-pore of 0.5-3nm for H.Li etc.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 kamash alloy particle 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 purpose of this invention is to provide metal particle-cladded active carbon microsphere cathode composite materials and preparation method thereof.This method is a presoma with phenolic resins, metal or oxide, prepares metal particle-cladded active carbon microsphere cathode composite materials by curing of reverse micelle emulsion and high-temperature process carbonizing reduction, and this method is simply direct, with low cost.
Metal particle-cladded active carbon microsphere cathode composite materials proposed by the invention is characterized in that, described metal is a storage lithium reactive metal, and described storage lithium reactive metal is blended 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 metal particle-cladded active carbon microsphere cathode composite materials 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) water soluble phenol resin is dissolved in the deionized water, adds the fine powder that obtains of curing agent and step (1), fully stir and obtain mixed resin solution; Wherein the quality of curing agent is 5%～15% of a phenolic resins, and the fine powder of adding and the mass ratio of phenolic resins are 0.2: 1～1: 1;
(3) above-mentioned mixed resin 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 described mixed resin solution and oil phase is 0.02: 1～0.1: 1, the reverse micelle emulsion that obtains stirs under 60 ℃～120 ℃ temperature, rotating speed is 200rpm～1200rpm, obtains the activated carbon microspheres with solid;
(4) change step (3) gained activated carbon 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 activated carbon microspheres with solid surface attachment;
(5) with step (4) products therefrom as in the reactor, under inert gas shielding, be warming up to 800 ℃～1200 ℃, isothermal reaction, natural cooling in reactor then obtains the spherical composite materials of particle-cladded active carbon microsphere storage lithium reactive 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 curing agent is hexamethylenetetramine or urea.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 particle-cladded active carbon microsphere tin.
Embodiment
Concrete scheme of the present invention is as follows:
(1) a certain amount of storage lithium reactive metal or their 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) water soluble phenol resin is dissolved in the deionized water, adds the fine powder that curing agent and step (1) obtain, fully stir and obtain mixed resin solution.Wherein the quality of curing agent is 5%～15% of a phenolic resins, and the fine powder of adding and the mass ratio of phenolic resins are 0.02: 1～1: 1.
(3) above-mentioned mixed resin 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 resin solution and oil phase is 0.02: 1～0.1: 1.The reverse micelle emulsion that obtains keeps 60 ℃～120 ℃ temperature that water-soluble resin is cured the reaction time enough under the rotating speed of 200rpm～1200rpm stirs, and obtains 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 metal particle-cladded active carbon microsphere.
Introduce embodiments of the invention below:
Example 1
5g water soluble phenol resin and 0.25g hexamethylenetetramine are dissolved in the 10mL deionized water SnO behind the adding 1g ball milling
2Powder fully stirs, and is scattered in the kerosene that 100mL contains 12g SPAN80 to form the reverse micelle emulsion.Under 60 ℃, rotating speed is that 200rpm is stirred to microspheres with solid and occurs, and 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 (see figure 1) of metal particle-cladded active carbon microsphere tin at last.Recording this product average grain diameter is 50～60 μ m, and metallic tin content is 35.2% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this particle-cladded active carbon microsphere tin composite material initial charge specific capacity at room temperature is 436mAh/g, and capability retention is 73.5% after 50 charge and discharge cycles.
Example 2
5g water soluble phenol resin and 0.5g hexamethylenetetramine are dissolved in the 10mL deionized water SnO behind the adding 3g ball milling
2Powder fully stirs, and is scattered in the kerosene that 400mL contains 15g SPAN80 to form the reverse micelle emulsion.Under 90 ℃, rotating speed is that 600rpm is stirred to microspheres with solid and occurs, and 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 metal particle-cladded active carbon microsphere tin at last.Recording this product average grain diameter is 20～30 μ m, and metallic tin content is 57.9% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this particle-cladded active carbon microsphere tin composite material initial charge specific capacity at room temperature is 582mAh/g, and capability retention is 70.8% after 50 charge and discharge cycles.
Example 3
5g water soluble phenol resin and 0.75g urea are dissolved in the 10mL deionized water SnO behind the adding 5g ball milling
2Powder fully stirs, and is scattered in the cyclohexylamine that 500mL contains 4g SPAN80 to form the reverse micelle emulsion.Under 120 ℃, rotating speed is that 1200rpm is stirred to microspheres with solid and occurs,, 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 metal particle-cladded active carbon microsphere tin at last.Recording this product average grain diameter is 60～80 μ m, and metallic tin content is 70.8% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this particle-cladded active carbon microsphere tin composite material initial charge specific capacity at room temperature is 718mAh/g, and capability retention is 62.3% after 50 charge and discharge cycles.
Example 4
5g water soluble phenol resin and 0.5g hexamethylenetetramine are dissolved in the 10mL deionized water SnO behind the adding 1g ball milling
2/ Sb
2O
3(present embodiment adopted mol ratio 2: 1, Sn, Sb are storage lithium metals, the two arbitrarily the alloy that forms of mol ratio all be available lithium ion battery negative material) mixed oxide powder, fully stir, be scattered in the cyclohexylamine that 400mL contains the 15g polysorbate60 and form the reverse micelle emulsion.Under 90 ℃, rotating speed is that 400rpm is stirred to microspheres with solid and occurs,, 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 900 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of particle-cladded active carbon microsphere tin pewter at last.Recording this product average grain diameter is 20～30 μ m, and tin pewter content is 38.5% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this particle-cladded active carbon microsphere tin pewter composite materials initial charge specific capacity at room temperature is 402mAh/g, and 50 times discharge and recharge the back capability retention is 85.1%.
Example 5
5g water soluble phenol resin and 0.75g hexamethylenetetramine are dissolved in the 10mL deionized water CuO/SnO behind the adding 3g ball milling
2Mixed 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 this alloy property of other ratio is all relatively poor), fully stir, be scattered in the cyclohexylamine that 400mL contains the 15g polysorbate60 and form the reverse micelle emulsion.Under 90 ℃, rotating speed is that 400rpm is stirred to microspheres with solid and occurs, and 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 1000 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of particle-cladded active carbon microsphere gun-metal at last.Recording this product average grain diameter is 30～40 μ m, and gun-metal content is 58.6% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this particle-cladded active carbon microsphere gun-metal composite materials initial charge specific capacity at room temperature is 332mAh/g, and capability retention is 89.5% after 50 charge and discharge cycles.
Example 6
5g water soluble phenol resin and 0.5g urea are dissolved in the 10mL deionized water SnO behind the adding 3g ball milling
2/ Sb
2O
3(present embodiment adopted mol ratio 4: 1, Sn, Sb are storage lithium metals, the two arbitrarily the alloy that forms of mol ratio all be available lithium ion battery negative material) mixed oxide powder, fully stir, be scattered in the cyclohexane that 400mL contains 15g TritonX X-200 and form the reverse micelle emulsion.Under 90 ℃, rotating speed is that 400rpm is stirred to microspheres with solid and occurs, and 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 900 ℃ then, constant temperature 2 hours, through resin carbonation and carbon thermal reduction process, natural cooling in stove obtains the spherical composite materials of particle-cladded active carbon microsphere tin pewter at last.Recording this product average grain diameter is 20～30 μ m, and tin pewter content is 65.7% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this particle-cladded active carbon microsphere tin pewter composite materials initial charge specific capacity at room temperature is 556mAh/g, and 50 times discharge and recharge the back capability retention is 83.6%.
Example 7
5g water soluble phenol resin and 0.5g hexamethylenetetramine are dissolved in the 10mL deionized water, add the Si powder behind the 3g ball milling, fully stir, be scattered in the kerosene that 400mL contains 15g SPAN80 and form the reverse micelle emulsion.Under 90 ℃, rotating speed is that 400rpm is stirred to microspheres with solid and occurs, and 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 particle-cladded active carbon microsphere silicon at last.Recording this product average grain diameter is 20～30 μ m, and silicone content is 68.9% (mass fraction) in the compound.With the lithium sheet is negative pole, and recording this particle-cladded active carbon microsphere silicon compound material initial charge specific capacity at room temperature is 1020mAh/g, and 50 times discharge and recharge the back capability retention is 78.1%.
Claims (8)
1, metal particle-cladded active carbon microsphere cathode composite materials is characterized in that, described metal is a storage lithium reactive metal, and described storage lithium reactive metal is blended in the active-carbon-microball, and its mass percent is 30%～80%.
2, metal particle-cladded active carbon microsphere cathode composite materials as claimed in claim 1 is characterized in that, described storage lithium reactive metal is a kind of among Sn, Sn/Sb alloy, Sn/Cu alloy or the Si.
3, the preparation method of metal particle-cladded active carbon microsphere cathode composite materials 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) water soluble phenol resin is dissolved in the deionized water, adds the fine powder that obtains of curing agent and step (1), fully stir and obtain mixed resin solution; Wherein the quality of curing agent is 5%～15% of a phenolic resins, and the fine powder of adding and the mass ratio of phenolic resins are 0.2: 1～1: 1;
(3) above-mentioned mixed resin 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 described mixed resin solution and oil phase is 0.02: 1～0.1: 1, the reverse micelle emulsion that obtains stirs under 60 ℃～120 ℃ temperature, rotating speed is 200rpm～1200rpm, obtains the activated carbon microspheres with solid;
(4) change step (3) gained activated carbon 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 activated carbon microspheres with solid surface attachment;
(5) with step (4) products therefrom as in the reactor, under inert gas shielding, be warming up to 800 ℃～1200 ℃, isothermal reaction, natural cooling in reactor then obtains the spherical composite materials of particle-cladded active carbon microsphere storage lithium reactive metal.
4, the preparation method of metal particle-cladded active carbon microsphere cathode composite materials as claimed in claim 3 is characterized in that, described storage lithium reactive metal is Si.
5, the preparation method of metal particle-cladded active carbon microsphere cathode composite materials as claimed in claim 3 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.
6, the preparation method of metal particle-cladded active carbon microsphere cathode composite materials as claimed in claim 3 is characterized in that, described curing agent is hexamethylenetetramine or urea.
7, the preparation method of metal particle-cladded active carbon microsphere cathode composite materials as claimed in claim 3 is characterized in that, described surfactant is a kind of among SPAN80, polysorbate60, the TritonX X-200.
8, the preparation method of metal particle-cladded active carbon microsphere cathode composite materials as claimed in claim 3 is characterized in that, described oil phase is a kind of in kerosene, cyclohexylamine or the cyclohexane.
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