CN103199227B - C/Si composite negative nanomaterial of lithium ion battery and preparation method of nanomaterial - Google Patents
C/Si composite negative nanomaterial of lithium ion battery and preparation method of nanomaterial Download PDFInfo
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- CN103199227B CN103199227B CN201310149926.2A CN201310149926A CN103199227B CN 103199227 B CN103199227 B CN 103199227B CN 201310149926 A CN201310149926 A CN 201310149926A CN 103199227 B CN103199227 B CN 103199227B
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 19
- 239000002086 nanomaterial Substances 0.000 title abstract 6
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 114
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 112
- 239000010703 silicon Substances 0.000 claims description 61
- 229910052710 silicon Inorganic materials 0.000 claims description 60
- 239000003610 charcoal Substances 0.000 claims description 49
- 239000010406 cathode material Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000008246 gaseous mixture Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002006 petroleum coke Substances 0.000 claims description 5
- 239000011295 pitch Substances 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 4
- 239000011294 coal tar pitch Substances 0.000 claims description 4
- 239000011331 needle coke Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 239000006253 pitch coke Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002153 silicon-carbon composite material Substances 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000006258 conductive agent Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract 5
- 229910052682 stishovite Inorganic materials 0.000 abstract 5
- 229910052905 tridymite Inorganic materials 0.000 abstract 5
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002077 nanosphere Substances 0.000 abstract 1
- 239000011206 ternary composite Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- 229910021392 nanocarbon Inorganic materials 0.000 description 12
- 238000010276 construction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 239000005543 nano-size silicon particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a C/Si composite negative nanomaterial of a lithium ion battery and a preparation method of the nanomaterial, and belongs to the lithium ion battery negative material technologies. The C/Si composite negative nanomaterial comprises nanoparticles with the particle size of 20 to 50nm; the silicon part has a Si/SiO2 composite structure prepared from SiO; the carbon part is prepared from an amphipathic carbon material; the carbon part coats the surface of the silicon part to form a C/SiO2/Si ternary composite structure; and the mass ratio of the amphipathic carbon material to SiO is 20:1 to 5:1. According to the invention, the electric conductivity of the Si/SiO2 composite material is improved greatly, and the use amount of a conductive agent is reduced by compositing the Si/SiO2 composite material with carbon nanospheres prepared from the amphipathic carbon material; and the negative cycling stability of the carbon-silicon composite negative nanomaterial is improved greatly in comparison with the conventional mode by using the Si/SiO2 composite material with high stability.
Description
Technical field
The present invention relates to a kind of material for the preparation of lithium ion battery negative and preparation method thereof, more particularly, the present invention relates to a kind of lithium ion cell nano charcoal silicon composite cathode material and preparation method thereof, belong to lithium ion battery negative material technology.
Background technology
Lithium rechargeable battery energy density is large, operating voltage is high, have extended cycle life, pollution-free, security performance good, make it be with a wide range of applications in the many-side such as portable electric appts, electric automobile, extensive energy storage, space technology, national defense industry, become the study hotspot of " 12 " period.
The structure of commercial lithium ion battery generally includes: positive pole, negative pole, barrier film, electrolyte, center terminal, positive wire, battery case, negative wire, insulating material, safety valve, temperature control terminal etc.Wherein, the research of negative material is one of key technology of lithium ion battery.Carbon electrode material causes worldwide extensive research and development with the structural stability of its height and good cycle performance, becomes the lithium ion battery negative material having realized commercial applications at present.
It is CN102351163A that State Intellectual Property Office discloses a publication number in 2012.2.15, name is called the patent of invention of " a kind of nano carbon microsphere cathode material of lithium ion cell and preparation method thereof ", disclose a kind of nano carbon microsphere cathode material of lithium ion cell and preparation method thereof in this patent, belong to lithium ion battery negative material technology.Nano carbon microsphere cathode material of lithium ion cell described in this invention is by the amphipathic Carbon Materials of coal tar pitch base, petroleum asphalt based amphipathic Carbon Materials, the amphipathic Carbon Materials of intermediate phase pitch-based, the amphipathic Carbon Materials of petroleum coke base, one among the amphipathic Carbon Materials of needle coke base and the amphipathic Carbon Materials of pitch coke base is through obtain solution, the steps such as stirring and rectifying separation are made, Nano carbon prepared by the present invention is micro-to be formed by the self assembly under capillary constraint of amphipathic Carbon Materials, therefore ball uniform particle sizes, good sphericity, as lithium ion battery negative material, there is high reversible capacity and excellent cycle performance.But above-mentioned material is single carbon cathode material, due to the capacity bottleneck of Carbon Materials, limit the further raising of material specific capacity.
With the graphite-phase ratio of existing market, silicium cathode in theory specific capacity can improve about 10 times, is about about 4000mAh/g.But what affect by discharge and recharge due to silicon volume changes greatly, electrode structure can be damaged, and therefore charge and discharge circulation life is shorter, be used alone be difficult to realize practical.In order to alleviate the destruction of silicium cathode in Lithium-ion embeding deintercalation process, using other materials to carry out coated to crystalline silicon is a kind of effective mode.Macrocell of Hitachi have developed the composite negative pole material with silicon dioxide and the coated crystalline silicon of charcoal, adopts silicon class material by negative pole, makes trendy battery capacity comparable the said firm original product improve 10%.Consider from the stability of negative material and the requirement of low cost, using Carbon Materials to carry out clad nano silicon grain is a kind of feasible method.The preparation method of charcoal silicon composite cathode material mainly comprises thermal decomposition method, sol-gel process, high-energy mechanical ball milling method and chemical vapour deposition technique etc.
It is CN102709532A that State Intellectual Property Office discloses a publication number in 2012.10.3, name is called the patent of " a kind of charcoal silicon composite cathode material for the preparation of lithium ion battery and preparation method thereof ", which disclose a kind of preparation method of charcoal silicon composite, this patent uses crystalline silicon to carry out with amphipathic Carbon Materials mixing, stirs, precipitates, freeze drying and carbonizing processes, and finally obtains the charcoal silicon composite of height ratio capacity.But the composite material in this invention is with Carbon Materials, crystalline silicon is coated, the contact interface of charcoal-silicon is not stablize especially, in charge and discharge process, the coefficient of expansion of silicon is comparatively large, likely can destroy the contact interface of silicon-charcoal, thus cause electrode material hydraulic performance decline.
It is CN102522534A that State Intellectual Property Office discloses a publication number in 2012.6.27, name is called " a kind of high-specific-capacity silicon carbon composite material and preparation method thereof, lithium ion battery negative material and lithium ion battery " patent, the lithium ion battery negative material which disclosing a kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof and use this material to prepare and lithium ion battery, this Si-C composite material comprises the porous carbon basis material with hole and is compounded in the interpore nano-silicon particle of these porous carbon basis materials, and the particle diameter of silicon nanoparticle is 5-100nm in Si-C composite material, wherein nano-silicon content is 10-90wt%, this Si-C composite material manufacture craft is simple, bulk effect during obvious reduction silicon-containing active material removal lithium embedded, improve the dispersal behavior of lithium in active material, improve the specific capacity of lithium ion battery, the cell negative electrode material prepared by this composite material conducts electricity very well, the lithium battery good cycle of preparation.
Said method needs to use hydrofluoric acid removing silicon dioxide in preparation process, due to hypertoxicity and the severe corrosive of hydrofluoric acid, can limit large-scale production and the application of this material greatly.In addition, the silicon dioxide that silicon monoxide pyrolysis produces is the structure that a kind of uniform close is combined with silicon, and silicon dioxide wherein can limit and alleviate the Volumetric expansion of silicon monoxide.This invention eliminates silicon dioxide, also just means and loses effect that silicon dioxide alleviates bulk effect.In the selection of carbon source, this patent have selected the carbon sources such as Graphene, carbon nano-tube, carbon fiber, acetylene black, expanded graphite, then mixes with silicon grain sonic oscillation.This compound uses physical method to make silicon grain be embedded in the hole of Carbon Materials, and be a kind of simple physical bond, bond strength is very little, therefore to the bulk effect limited efficiency alleviating silicon.
Summary of the invention
The present invention is intended to solve the problems of the prior art, provides one to meet market to the long-life demand of lithium ion battery height ratio capacity, and promote the overall performance of lithium battery, development cost is cheap, is suitable for the Nano carbon silicon composite cathode material of volume production.
Another object of the present invention, for providing the optimized fabrication method of above-mentioned composite negative pole material, reaches that composite material conjugation is high, technique cheap and simple, is easy to the object of volume production.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
A kind of lithium ion cell nano charcoal silicon composite cathode material, is characterized in that: the nano particle of described Nano carbon silicon composite cathode material to be particle diameter be 20-50nm; Silicon part is the composite construction of silicon and the silicon dioxide be prepared from by silicon monoxide; Charcoal part is for be prepared from by amphipathic Carbon Materials; Described charcoal part is coated on silicon part surface, forms triple composite constructions of charcoal, silicon dioxide and silicon; Described amphipathic Carbon Materials and the mass ratio of silicon monoxide are 20:1-5:1.
The above-mentioned material 1C capacity first that discharges reaches 820mAh/g, and in 8C multiplying power discharging situation, capacity is not less than 670mAh/g.
Preferably, amphipathic Carbon Materials of the present invention is one or more the arbitrary proportion mixture in the amphipathic Carbon Materials of coal tar pitch base, petroleum asphalt based amphipathic Carbon Materials, the amphipathic Carbon Materials of intermediate phase pitch-based, the amphipathic Carbon Materials of petroleum coke base, the amphipathic Carbon Materials of needle coke base and the amphipathic Carbon Materials of pitch coke base.
Preferably, a kind of preparation method of lithium ion cell nano charcoal silicon composite cathode material, is characterized in that: comprise following processing step:
A, amphipathic Carbon Materials is joined in deionized water, be mixed with amphipathic Carbon Materials solution, then regulate amphipathic Carbon Materials solution for alkalescence, obtain alkaline amphipathic Carbon Materials solution;
B, take silicon monoxide powder by the mass ratio 20:1-5:1 of amphipathic Carbon Materials and silicon monoxide, silicon monoxide powder is added in the amphipathic Carbon Materials solution of the alkalescence obtained in steps A, be disperse 0.5-5h under the stirring state of 800-1500r/min at rotating speed, obtain mixed liquor;
C, when stir, drip the pH value of the mixed liquor that sour regulating step B obtains, make the pH value of this mixed liquor lower than 6, stop stirring, leave standstill 1-10h, liquid layered, upper strata is containing acidic aqueous solution, and lower floor is containing amphipathic Carbon Materials and silicon monoxide mixture particulate;
D, the upper strata obtained by step C are separated with lower floor, and the amphipathic Carbon Materials using washed with de-ionized water lower floor to obtain and silicon monoxide mixture particulate;
E, the amphipathic Carbon Materials that obtains will be separated through step D and silicon monoxide mixture particle spray is dry, obtain black gray expandable powder;
F, in heating furnace, under an inert atmosphere black gray expandable powder is risen to 800-1300 DEG C with the heating rate of 0.5-5 DEG C/min heat-treat 0.5-2h, silicon monoxide generation disproportionated reaction, obtain the compound of silicon dioxide and silicon, then room temperature is naturally cooled to, obtain nano particle, i.e. lithium ion cell nano charcoal silicon composite cathode material.
Preferably, in step, the mass concentration of described amphipathic Carbon Materials solution is 5-10% in the present invention.
Preferably, in step, the amphipathic Carbon Materials solution of described adjustment is that to be specially by water-soluble alkali adjust ph be 10-14 to alkalescence in the present invention.
Preferably, the present invention is in step C, and the rotating speed of described stirring is 800-1500r/min.
Preferably, the present invention is in step C, and described acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid or phosphoric acid.
Preferably, the present invention is in step F, and described inert atmosphere is the gaseous mixture of nitrogen, helium and hydrogen, argon gas and the gaseous mixture of hydrogen or the gaseous mixture of argon gas and hydrogen.
Preferably, the present invention is in step F, and described heat treatment uses tube furnace, box type furnace or rotary furnace.
The Advantageous Effects that the present invention brings:
1, lithium ion cell nano charcoal silicon composite cathode material of the present invention is by Si/SiO
2composite material carries out compound with the Nano carbon microballoon be made up of amphipathic Carbon Materials, improves Si/SiO greatly
2the conductivity of composite material, reduces conductive agent consumption, also utilizes Si/SiO simultaneously
2the high stability of composite material makes negative pole cyclical stability greatly improve than traditional " charcoal bag silicon " pattern; Silicon dioxide is as the interfaces transition of carbon and silicon, and this will improve the bond strength of several material greatly, alleviates the bulk effect of silicon in removal lithium embedded process to a greater degree; The initial feed such as the pitch that the present invention uses, petroleum coke are cheap, abundance, are easy to realize large-scale industrial and produce;
2, the lithium ion cell nano charcoal silicon composite cathode material specific capacity prepared of the present invention is high, cyclical stability is excellent, good rate capability, this material 1C capacity first that discharges reaches 820mAh/g after tested, and capacity is still not less than 670mAh/g in the large multiplying power discharging situation of 8C, efficiency is not less than 85% first, through 200 circulation volume conservation rates more than 85%;
3, preferred synthesis technique of the present invention and the equipment of use simple, compared with the synthetic method of Conventional nano silicon and Nano carbon as hydro thermal method, template etc., production cost is more cheap; What the present invention taked is that carbon source and silicon source are jointly sintered combined forms, simple physical not in background technology combines, and there is silicon dioxide as the interfaces transition of carbon and silicon, this will improve the bond strength of several material greatly, alleviates the bulk effect of silicon in removal lithium embedded process to a greater degree;
4, the patent in background technology is added by organic solvent and makes amphipathic Carbon Materials precipitate into cohesion, allows solution layering, and adjustment in use pH of the present invention reaches this effect, avoids the use of organic solvent; Patent in background technology uses solvent exchange method dry again to ensure that nano particle is not reunited, and the present invention uses spray-dired method to reach this effect, simplifies technique, has saved cost, has shortened generated time.
Embodiment
embodiment 1
A kind of lithium ion cell nano charcoal silicon composite cathode material, the nano particle of described Nano carbon silicon composite cathode material to be particle diameter be 20nm; Silicon part is the composite construction of silicon and the silicon dioxide be prepared from by silicon monoxide; Charcoal part is for be prepared from by amphipathic Carbon Materials; Described charcoal part is coated on silicon part surface, forms triple composite constructions of charcoal, silicon dioxide and silicon; Described amphipathic Carbon Materials and the mass ratio of silicon monoxide are 5:1.
The above-mentioned material 1C capacity first that discharges reaches 820mAh/g, and in 8C multiplying power discharging situation, capacity is not less than 670mAh/g.
embodiment 2
A kind of lithium ion cell nano charcoal silicon composite cathode material, the nano particle of described Nano carbon silicon composite cathode material to be particle diameter be 50nm; Silicon part is the composite construction of silicon and the silicon dioxide be prepared from by silicon monoxide; Charcoal part is for be prepared from by amphipathic Carbon Materials; Described charcoal part is coated on silicon part surface, forms triple composite constructions of charcoal, silicon dioxide and silicon; Described amphipathic Carbon Materials and the mass ratio of silicon monoxide are 20:1.
The above-mentioned material 1C capacity first that discharges reaches 820mAh/g, and in 8C multiplying power discharging situation, capacity is not less than 670mAh/g.
embodiment 3
A kind of lithium ion cell nano charcoal silicon composite cathode material, the nano particle of described Nano carbon silicon composite cathode material to be particle diameter be 35nm; Silicon part is the composite construction of silicon and the silicon dioxide be prepared from by silicon monoxide; Charcoal part is for be prepared from by amphipathic Carbon Materials; Described charcoal part is coated on silicon part surface, forms triple composite constructions of charcoal, silicon dioxide and silicon; Described amphipathic Carbon Materials and the mass ratio of silicon monoxide are 13:1.
The above-mentioned material 1C capacity first that discharges reaches 820mAh/g, and in 8C multiplying power discharging situation, capacity is not less than 670mAh/g.
embodiment 4
A kind of lithium ion cell nano charcoal silicon composite cathode material, the nano particle of described Nano carbon silicon composite cathode material to be particle diameter be 45nm; Silicon part is the composite construction of silicon and the silicon dioxide be prepared from by silicon monoxide; Charcoal part is for be prepared from by amphipathic Carbon Materials; Described charcoal part is coated on silicon part surface, forms triple composite constructions of charcoal, silicon dioxide and silicon; Described amphipathic Carbon Materials and the mass ratio of silicon monoxide are 10:1.
The above-mentioned material 1C capacity first that discharges reaches 820mAh/g, and in 8C multiplying power discharging situation, capacity is not less than 670mAh/g.
embodiment 5
On the basis of embodiment 1-4:
Preferably, described amphipathic Carbon Materials is one or more the arbitrary proportion mixture in the amphipathic Carbon Materials of coal tar pitch base, petroleum asphalt based amphipathic Carbon Materials, the amphipathic Carbon Materials of intermediate phase pitch-based, the amphipathic Carbon Materials of petroleum coke base, the amphipathic Carbon Materials of needle coke base and the amphipathic Carbon Materials of pitch coke base.
embodiment 6
The optimized fabrication method of a kind of lithium ion cell nano charcoal of the present invention silicon composite cathode material:
A, amphipathic Carbon Materials is joined in deionized water, be mixed with amphipathic Carbon Materials solution, then regulate amphipathic Carbon Materials solution for alkalescence, obtain alkaline amphipathic Carbon Materials solution;
B, take silicon monoxide powder by the mass ratio 5:1 of amphipathic Carbon Materials and silicon monoxide, silicon monoxide powder is added in the amphipathic Carbon Materials solution of the alkalescence obtained in steps A, be disperse 0.5h under the stirring state of 800r/min at rotating speed, obtain mixed liquor;
C, when stirring, dripping the pH value of the mixed liquor that sour regulating step B obtains, making the pH value of this mixed liquor be 2, stop stirring, leave standstill 1h, liquid layered, upper strata is containing acidic aqueous solution, and lower floor is containing amphipathic Carbon Materials and silicon monoxide mixture particulate;
D, the upper strata obtained by step C are separated with lower floor, and the amphipathic Carbon Materials using washed with de-ionized water lower floor to obtain and silicon monoxide mixture particulate;
E, the amphipathic Carbon Materials that obtains will be separated through step D and silicon monoxide mixture particle spray is dry, obtain black gray expandable powder;
F, in heating furnace, under an inert atmosphere black gray expandable powder is risen to 800 DEG C with the heating rate of 0.5 DEG C/min heat-treat 0.5h, silicon monoxide generation disproportionated reaction, obtain the compound of silicon dioxide and silicon, then room temperature is naturally cooled to, obtain nano particle, i.e. lithium ion cell nano charcoal silicon composite cathode material.
embodiment 7
The optimized fabrication method of a kind of lithium ion cell nano charcoal of the present invention silicon composite cathode material:
A, amphipathic Carbon Materials is joined in deionized water, be mixed with amphipathic Carbon Materials solution, then regulate amphipathic Carbon Materials solution for alkalescence, obtain alkaline amphipathic Carbon Materials solution;
B, take silicon monoxide powder by the mass ratio 20:1 of amphipathic Carbon Materials and silicon monoxide, silicon monoxide powder is added in the amphipathic Carbon Materials solution of the alkalescence obtained in steps A, be disperse 5h under the stirring state of 1500r/min at rotating speed, obtain mixed liquor;
C, when stirring, dripping the pH value of the mixed liquor that sour regulating step B obtains, making the pH value of this mixed liquor be 5, stop stirring, leave standstill 10h, liquid layered, upper strata is containing acidic aqueous solution, and lower floor is containing amphipathic Carbon Materials and silicon monoxide mixture particulate;
D, the upper strata obtained by step C are separated with lower floor, and the amphipathic Carbon Materials using washed with de-ionized water lower floor to obtain and silicon monoxide mixture particulate;
E, the amphipathic Carbon Materials that obtains will be separated through step D and silicon monoxide mixture particle spray is dry, obtain black gray expandable powder;
F, in heating furnace, under an inert atmosphere black gray expandable powder is risen to 1300 DEG C with the heating rate of 5 DEG C/min heat-treat 2h, silicon monoxide generation disproportionated reaction, obtain the compound of silicon dioxide and silicon, then room temperature is naturally cooled to, obtain nano particle, i.e. lithium ion cell nano charcoal silicon composite cathode material.
embodiment 8
The optimized fabrication method of a kind of lithium ion cell nano charcoal of the present invention silicon composite cathode material:
A, amphipathic Carbon Materials is joined in deionized water, be mixed with amphipathic Carbon Materials solution, then regulate amphipathic Carbon Materials solution for alkalescence, obtain alkaline amphipathic Carbon Materials solution;
B, take silicon monoxide powder by the mass ratio 13:1 of amphipathic Carbon Materials and silicon monoxide, silicon monoxide powder is added in the amphipathic Carbon Materials solution of the alkalescence obtained in steps A, be disperse 2.75h under the stirring state of 1150r/min at rotating speed, obtain mixed liquor;
C, when stirring, dripping the pH value of the mixed liquor that sour regulating step B obtains, making the pH value of this mixed liquor be 3, stop stirring, leave standstill 5.5h, liquid layered, upper strata is containing acidic aqueous solution, and lower floor is containing amphipathic Carbon Materials and silicon monoxide mixture particulate;
D, the upper strata obtained by step C are separated with lower floor, and the amphipathic Carbon Materials using washed with de-ionized water lower floor to obtain and silicon monoxide mixture particulate;
E, the amphipathic Carbon Materials that obtains will be separated through step D and silicon monoxide mixture particle spray is dry, obtain black gray expandable powder;
F, in heating furnace, under an inert atmosphere black gray expandable powder is risen to 1050 DEG C with the heating rate of 2.75 DEG C/min heat-treat 1.25h, silicon monoxide generation disproportionated reaction, obtain the compound of silicon dioxide and silicon, then room temperature is naturally cooled to, obtain nano particle, i.e. lithium ion cell nano charcoal silicon composite cathode material.
embodiment 9
The optimized fabrication method of a kind of lithium ion cell nano charcoal of the present invention silicon composite cathode material:
A, amphipathic Carbon Materials is joined in deionized water, be mixed with amphipathic Carbon Materials solution, then regulate amphipathic Carbon Materials solution for alkalescence, obtain alkaline amphipathic Carbon Materials solution;
B, take silicon monoxide powder by the mass ratio 18:1 of amphipathic Carbon Materials and silicon monoxide, silicon monoxide powder is added in the amphipathic Carbon Materials solution of the alkalescence obtained in steps A, be disperse 4h under the stirring state of 1200r/min at rotating speed, obtain mixed liquor;
C, when stirring, dripping the pH value of the mixed liquor that sour regulating step B obtains, making the pH value of this mixed liquor be 4, stop stirring, leave standstill 8h, liquid layered, upper strata is containing acidic aqueous solution, and lower floor is containing amphipathic Carbon Materials and silicon monoxide mixture particulate;
D, the upper strata obtained by step C are separated with lower floor, and the amphipathic Carbon Materials using washed with de-ionized water lower floor to obtain and silicon monoxide mixture particulate;
E, the amphipathic Carbon Materials that obtains will be separated through step D and silicon monoxide mixture particle spray is dry, obtain black gray expandable powder;
F, in heating furnace, under an inert atmosphere black gray expandable powder is risen to 900 DEG C with the heating rate of 1 DEG C/min heat-treat 1.75h, silicon monoxide generation disproportionated reaction, obtain the compound of silicon dioxide and silicon, then room temperature is naturally cooled to, obtain nano particle, i.e. lithium ion cell nano charcoal silicon composite cathode material.
embodiment 10
On the basis of embodiment 6-9, preferred:
In step, the mass concentration of described amphipathic Carbon Materials solution is 5%.
In step, the amphipathic Carbon Materials solution of described adjustment is that to be specially by water-soluble alkali adjust ph be 10 to alkalescence.
In step C, the rotating speed of described stirring is 800r/min.
In step C, described acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid or phosphoric acid.
In step F, described inert atmosphere is the gaseous mixture of nitrogen, helium and hydrogen, argon gas and the gaseous mixture of hydrogen or the gaseous mixture of argon gas and hydrogen.
In step F, described heat treatment uses tube furnace, box type furnace or rotary furnace.
embodiment 11
On the basis of embodiment 6-9, preferred:
In step, the mass concentration of described amphipathic Carbon Materials solution is 10%.
In step, the amphipathic Carbon Materials solution of described adjustment is that to be specially by water-soluble alkali adjust ph be 14 to alkalescence.
In step C, the rotating speed of described stirring is 1500r/min.
In step C, described acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid or phosphoric acid.
In step F, described inert atmosphere is the gaseous mixture of nitrogen, helium and hydrogen, argon gas and the gaseous mixture of hydrogen or the gaseous mixture of argon gas and hydrogen.
In step F, described heat treatment uses tube furnace, box type furnace or rotary furnace.
embodiment 12
On the basis of embodiment 6-9, preferred:
In step, the mass concentration of described amphipathic Carbon Materials solution is 7.5%.
In step, the amphipathic Carbon Materials solution of described adjustment is that to be specially by water-soluble alkali adjust ph be 12 to alkalescence.
In step C, the rotating speed of described stirring is 1150r/min.
In step C, described acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid or phosphoric acid.
In step F, described inert atmosphere is the gaseous mixture of nitrogen, helium and hydrogen, argon gas and the gaseous mixture of hydrogen or the gaseous mixture of argon gas and hydrogen.
In step F, described heat treatment uses tube furnace, box type furnace or rotary furnace.
embodiment 13
On the basis of embodiment 6-9, preferred:
In step, the mass concentration of described amphipathic Carbon Materials solution is 8%.
In step, the amphipathic Carbon Materials solution of described adjustment is that to be specially by water-soluble alkali adjust ph be 13 to alkalescence.
In step C, the rotating speed of described stirring is 1000r/min.
In step C, described acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid or phosphoric acid.
In step F, described inert atmosphere is the gaseous mixture of nitrogen, helium and hydrogen, argon gas and the gaseous mixture of hydrogen or the gaseous mixture of argon gas and hydrogen.
In step F, described heat treatment uses tube furnace, box type furnace or rotary furnace.
Claims (7)
1. a preparation method for lithium ion cell nano charcoal silicon composite cathode material, is characterized in that: comprise following processing step:
A, amphipathic Carbon Materials is joined in deionized water, be mixed with amphipathic Carbon Materials solution, then regulate amphipathic Carbon Materials solution for alkalescence, obtain alkaline amphipathic Carbon Materials solution; The mass concentration of described amphipathic Carbon Materials solution is 5-10%;
B, take silicon monoxide powder by the mass ratio 20:1-5:1 of amphipathic Carbon Materials and silicon monoxide, silicon monoxide powder is added in the amphipathic Carbon Materials solution of the alkalescence obtained in steps A, be disperse 0.5-5h under the stirring state of 800-1500r/min at rotating speed, obtain mixed liquor;
C, when stir, drip the pH value of the mixed liquor that sour regulating step B obtains, make the pH value of this mixed liquor lower than 6, stop stirring, leave standstill 1-10h, liquid layered, upper strata is containing acidic aqueous solution, and lower floor is containing amphipathic Carbon Materials and silicon monoxide mixture particulate;
D, the upper strata obtained by step C are separated with lower floor, and the amphipathic Carbon Materials using washed with de-ionized water lower floor to obtain and silicon monoxide mixture particulate;
E, the amphipathic Carbon Materials that obtains will be separated through step D and silicon monoxide mixture particle spray is dry, obtain black gray expandable powder;
F, in heating furnace, under an inert atmosphere black gray expandable powder is risen to 800-1300 DEG C with the heating rate of 0.5-5 DEG C/min heat-treat 0.5-2h, silicon monoxide generation disproportionated reaction, obtain the compound of silicon dioxide and silicon, then room temperature is naturally cooled to, obtain nano particle, i.e. lithium ion cell nano charcoal silicon composite cathode material.
2. the preparation method of a kind of lithium ion cell nano charcoal silicon composite cathode material according to claim 1, is characterized in that: described amphipathic Carbon Materials is one or more the arbitrary proportion mixture in the amphipathic Carbon Materials of coal tar pitch base, petroleum asphalt based amphipathic Carbon Materials, the amphipathic Carbon Materials of intermediate phase pitch-based, the amphipathic Carbon Materials of petroleum coke base, the amphipathic Carbon Materials of needle coke base and the amphipathic Carbon Materials of pitch coke base.
3. the preparation method of a kind of lithium ion cell nano charcoal silicon composite cathode material according to claim 1, is characterized in that: in step, and the amphipathic Carbon Materials solution of described adjustment is that to be specially by water-soluble alkali adjust ph be 10-14 to alkalescence.
4. the preparation method of a kind of lithium ion cell nano charcoal silicon composite cathode material according to claim 1, is characterized in that: in step C, and the rotating speed of described stirring is 800-1500r/min.
5. the preparation method of a kind of lithium ion cell nano charcoal silicon composite cathode material according to claim 1, it is characterized in that: in step C, described acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid or phosphoric acid.
6. the preparation method of a kind of lithium ion cell nano charcoal silicon composite cathode material according to claim 1, it is characterized in that: in step F, described inert atmosphere is the gaseous mixture of nitrogen, helium and hydrogen, argon gas and the gaseous mixture of hydrogen or the gaseous mixture of argon gas and hydrogen.
7. the preparation method of a kind of lithium ion cell nano charcoal silicon composite cathode material according to claim 1, is characterized in that: in step F, and described heat treatment uses tube furnace, box type furnace or rotary furnace.
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| CN109301232A (en) * | 2018-10-08 | 2019-02-01 | 成都爱敏特新能源技术有限公司 | A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method |
| CN110627034B (en) * | 2019-07-31 | 2021-07-06 | 宁波中车新能源科技有限公司 | Preparation method of dual-functional energy-storage porous carbon-coated graphite composite material |
| CN111430676B (en) * | 2019-09-29 | 2022-06-21 | 蜂巢能源科技有限公司 | Negative electrode material of lithium ion battery and preparation method thereof |
| CN111653738B (en) * | 2020-04-20 | 2022-01-07 | 万向一二三股份公司 | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof |
| CN115028169B (en) * | 2022-08-11 | 2022-10-25 | 山东理工大学 | Preparation method of porous silicon monoxide negative electrode material for lithium ion battery |
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| CN102447112A (en) * | 2011-11-30 | 2012-05-09 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material, preparation method thereof, negative electrode material containing silicon-carbon composite material and lithium ion battery |
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