CN1601786A - Oxygen-contg composite carbon material for secondary lithium cell, its prepn process and usage - Google Patents

Oxygen-contg composite carbon material for secondary lithium cell, its prepn process and usage Download PDF

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Publication number
CN1601786A
CN1601786A CNA031600506A CN03160050A CN1601786A CN 1601786 A CN1601786 A CN 1601786A CN A031600506 A CNA031600506 A CN A031600506A CN 03160050 A CN03160050 A CN 03160050A CN 1601786 A CN1601786 A CN 1601786A
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carbon
lithium battery
oxide
oxygen complex
carbon material
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吴晓东
胡进
黄学杰
陈立泉
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Institute of Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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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  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to composite carbon material containing oxygen in use for quadric lithium cell including (1) Nano oxide, (2) carbon materials, and (3) hydrogen. Expression of Nano oxide is M1x1M2x2...Mnxn, containing 0.1-70wt%; carbon materials include each kind of carbon material; average size of composite carbon material containing oxygen is 1nm-500um; average size of nano oxide is 0.1nm-l00nm; hydrogen contains 5wt%. The disclosed material is suitable to be as cathode active material possessing high specific capacity, higher electric potential, efficiency for the first time, and long cycle life.

Description

What be used for serondary lithium battery contains oxygen complex carbon material and its production and use
Technical field
The present invention relates to a kind of be used for serondary lithium battery contain oxygen complex carbon material and its production and use, specifically relate to a kind of complex carbon material that contains oxidate nano disperse phase of the negative material of using as lithium ion battery, and its production and use.
Technical background
In the secondary lithium battery cathode active material, the theoretical specific capacity of lithium metal is 3830mAh/g, and is therefore the highest as the serondary lithium battery energy density of negative active core-shell material with lithium metal.But dendritic growth appears in lithium anode in charge and discharge process, make internal short-circuit of battery, causes battery burning even blast.In order to improve its fail safe, arrive late nineteen eighties at early seventies, lithium alloys such as lithium aluminium, lithium silicon, lithium lead, lithium tin, lithium cadmium once were used for the substituted metal lithium and made negative active core-shell material, though this has been avoided the dendritic growth problem to a certain extent, but these alloys can be because volumetric expansion and contraction and efflorescence gradually, i.e. dimension instability in the repeated charge process.As A Bailahan at the electrochemistry journal, 138 volumes, 1233 pages, 1993 described, efflorescence causes the variation that electrically contacts between alloy particle and the collector and between the alloy particle, causes battery performance to degenerate even loses efficacy.
In March, 1989, Japanese Sony Corporation has applied for that employing carbon makes negative active core-shell material, LiCoO 2Make the patent of the serondary lithium battery of positive electrode active materials, and in 1992 at first with its commercialization.Use carbon to solve the dendrite problem that causes in the lithium metal cyclic process as negative material, efflorescence with embedding lithium metal or alloy, (theoretical specific capacity of graphite-like material with carbon element is 372mAh/g but its capacity descends greatly, have only 340mAh/g in the actual use), this can not satisfy people far away to the highdensity requirement of cell high-capacity.
People such as dawn are at the science magazine, and 270 roll up, and 590 pages, nineteen ninety-five proposes to utilize the negative material of hard carbon material as lithium ion battery.Wang Maozhang etc. are in " manufacturing of carbon fiber, character and application thereof ", Science Press, and the 251-273 page or leaf is also pointed out can be by pyrolysis such as carbohydrate, resinae, the hard carbon that materials such as plant cellulose obtain is as the negative active core-shell material of lithium ion battery.But the impalpable structure of hard carbon material can provide more embedding lithium position, can break through the capacity limit of graphite-like material with carbon element, reach the above specific capacity of 400mAh/g, but having greatly in the material, embedding lithium capacity will could obtain at the current potential (near the deposition potential of lithium metal) lower than graphite embedding lithium current potential, in actual battery, be easy to cause separating out of lithium metal, cause safety problem outstanding.On the other hand, because embedding lithium current potential is low, adds the polarization phenomena in the battery discharge procedure, make the behavior of actual embedding lithium occur in below zero volt, this has just greatly reduced the actual active volume of hard carbon material, and promptly actual specific capacity is by being reduced to not enough 250mAh/g more than the 400mAh/g.
Mixing elements such as B, N, S, P in material with carbon element has a significant impact the performance of electrode material.For example in material with carbon element, mix a small amount of B element, can improve the embedding current potential of lithium, thereby improved the specific capacity of material.The adding of N element can improve the potential curve of material with carbon element, and is also helpful for the raising of capacity.But it is limited that capacity improves, and is no more than 50mAh/g.
Company of Fuji once proposed to use the tinbase composite oxides as lithium cell cathode material.The activated centre of this composite oxide material is a tin, and material metallic tin when discharging first is reduced out, and the charge and discharge process afterwards is actually the alloying reaction of tin and lithium.This material is forming lithia in the discharge process first, and formed lithia can not be decomposed in charging process, so the irreversible capacity first of material is very big.Because the alloying reaction change in volume in the material is huge, the cyclicity of material is restricted simultaneously.Company of Fuji has abandoned the research of this material at present.
Summary of the invention
The objective of the invention is to overcome the dendrite problem that secondary lithium battery cathode active material use lithium metal causes in the prior art and cause potential safety hazard, the cyclicity of using embedding lithium metal or alloy to bring is poor, the efficient first of using the embedding lithium metal oxide to be caused is low, use hard carbon material reality can utilize capacity low, cause the shortcoming of safety problem easily, a kind of height ratio capacity that both had is provided, higher embedding lithium current potential is arranged again, thereby can avoid potential safety hazard, have simultaneously high efficient first and long circulation life be used for serondary lithium battery contain the oxygen complex carbon material.
Another object of the present invention is to provide a kind of described preparation method who contains the oxygen complex carbon material who is used for serondary lithium battery.
A further object of the present invention be to provide a kind of described be used for serondary lithium battery contain the oxygen complex carbon material in the purposes of serondary lithium battery as negative material.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of be used for serondary lithium battery contain the oxygen complex carbon material, comprising:
1) nano-oxide;
With 2) material with carbon element;
It is 0.1～70wt% that nano-oxide accounts for the percentage by weight that contains the oxygen complex carbon material;
The expression formula of described nano-oxide is M 1 X1M 2 X2M n XnO x, M wherein 1, M 2M nRepresent different elements, be selected from Li, Be, N, Na, Mg, B, Al, Si, P, S, Se, Te, K, Ca in the major element, or the Sc of transition metal, Ti, V, Cr, Mn, Rb, Sr, Y, Zr, Nb, Mo, W, Ta, Hf, La, Ba, Cs, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Subscript x1, x2 ... xn, x represent the molar percentage of different element atoms, and x1+x2+ ... + xn+x=1;
Described material with carbon element comprises various carbon class materials, comprises native graphite, graphitization or not graphitization mesocarbon bead, needle coke, petroleum coke, the hard charcoal ball of micropore, carbon fiber, low temperature pyrogenation carbon, carbon black, active carbon, porous carbon, carbon molecular sieve.
The described average-size that contains the oxygen complex carbon material that is used for serondary lithium battery is 1nm～500um.
The average-size of described nano-oxide is 0.1nm～100nm.
Described nano-oxide is B 0.4O 0.6, H 0.1P 0.2O 0.7, S 0.33O 0.67, N 0.4O 0.6, Al 0.4O 0.6, Na 0.67O 0.33, Be 0.5O 0.5, K 0.67O 0.33, Ca 0.5O 0.5, V 0.33O 0.67, Si 0.33O 0.67, Si 0.33O 0.67, Ti 0.33O 0.67, Sc 0.4O 0.6, Y 0.4O 0.6, Zr 0.33O 0.67, Mo 0.25O 0.75, W 0.25O 0.75, Cr 0.25O 0.75, Sr 0.5O 0.5, Ce 0.33O 0.67, Nb 0.5O 0.5, Al 0.25Si 0.25O 0.5, Si 0.3Al 0.08C 0.62, Si 0.35Mg 0.28O 0.37
The invention provides described be used for serondary lithium battery contain the oxygen complex carbon material, also comprise:
3) hydrogen;
Hydrogen account for contain the oxygen complex carbon material percentage by weight less than 5wt%.
The invention provides a kind of described preparation method who contains the oxygen complex carbon material one who is used for serondary lithium battery, add the material that oxide maybe can be decomposed to form oxide in the predecessor of carbon, carbonization obtains composite material then.
The invention provides the another kind of described preparation method who contains the oxygen complex carbon material two who is used for serondary lithium battery, utilization contains the hetero-atom organic carbon and obtains composite material.
The invention provides the another kind of described preparation method who contains the oxygen complex carbon material three who is used for serondary lithium battery, use material with carbon element and oxide to be target, deposit in substrate by sputtering method and obtain composite material.
The invention provides the another kind of described preparation method who contains the oxygen complex carbon material four who is used for serondary lithium battery, utilize to be added with the method for carbon matrix precursor by chemical vapour deposition (CVD) that oxide maybe can be decomposed to form the material of oxide and to obtain composite material.
The invention provides the another kind of described preparation method who contains the oxygen complex carbon material five who is used for serondary lithium battery, utilize high-energy ball milling that the material that material with carbon element and oxide maybe can be decomposed to form oxide is carried out obtaining after the mechanical mixture.
The invention provides the another kind of described preparation method who contains the oxygen complex carbon material six who is used for serondary lithium battery, use the oxide of nanoscale to obtain after the surface carbon coating at low temperatures.
The invention provides the another kind of described preparation method who contains the oxygen complex carbon material seven who is used for serondary lithium battery, material with carbon element oxidation in the oxidizing atmosphere of gentleness is obtained.
The invention provides a kind of described be used for serondary lithium battery contain oxygen complex carbon material purposes, it forms serondary lithium battery as the secondary lithium battery cathode active material with the transition metal oxide positive pole that contains lithium, organic electrolyte solution, barrier film, battery case, collector and lead-in wire; Wherein, by barrier film that has soaked organic electrolyte solution or use polymer electrolyte is separated between positive pole and the negative pole, positive pole is burn-on respectively to go between on collector with an end of negative pole and is linked to each other with the battery case two ends of mutually insulated.
The positive electrode active materials that is used for serondary lithium battery of the present invention is the known material that is used for anode of secondary lithium battery, can reversibly embed and deviate from the transition metal oxide that contains lithium of lithium, typical in lithium and cobalt oxides, lithium nickel oxide or lithium manganese oxide etc.
The organic electrolyte solution that is used for serondary lithium battery of the present invention is the general electrolyte of serondary lithium battery, adds one or more solvable lithium salts in the mixed solvent that can be made up of a kind of organic solvent or several organic solvent and forms.Typical organic solvent is vinyl carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester or dimethoxy-ethane etc. for example; Typical solvable lithium salts such as lithium perchlorate, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium or hexafluoroarsenate lithium etc.; Typical system is dissolved in as 1 mole of lithium hexafluoro phosphate in 1 liter the propylene carbonate, 1 mole of lithium hexafluoro phosphate is dissolved in 1 liter volume ratio be in 3: 7 vinyl carbonate and the dimethyl carbonate or 1 mole of lithium hexafluoro phosphate to be dissolved in 1 liter dimethyl carbonate medium.
The barrier film that is used for serondary lithium battery of the present invention is the general barrier film of serondary lithium battery, as porous polypropylene barrier film or porous polyethylene barrier film etc.
Among the present invention is industrial general preparation method with the complex carbon material that contains nano-oxide as the secondary lithium battery cathode preparation method of negative active core-shell material: the complex carbon material and the conductive additive that will contain nano-oxide mix, and evenly are mixed and made into the composite material slurries at normal temperatures and pressures with adhesive again.Wherein conductive additive refers in the lithium ion battery material of increase active material conductivity commonly used, and as carbon black, acetylene black, graphite powder, metal powder or wire etc., the percentage by weight of itself and active material is 0% to 15%.Adhesive comprises solution or emulsion, for example, polytetrafluoroethylene is mixed the emulsion that forms with water, or Kynoar is dissolved in the solution that cyclohexane forms.Aforesaid composite material slurries are coated in paper tinsel, net, porous body or corpus fibrosum material as the various conductions of collector equably, on carriers such as Copper Foil, nickel screen, nickel foam or carbon felt, the gained film thickness is about 10-150 μ m, then film being dried down at 100 ℃-150 ℃, is 1-60Kg/cm at pressure 2Under compress, continue 100 ℃-150 ℃ bakings 1-12 hour the 2%-15% of oven dry back binder constitutes total weight.Be cut into different shape by the prepared cell specification and be negative pole.
Compared with the prior art the complex carbon material that contains nano-oxide provided by the invention, has tangible advantage:
The present invention uses material with carbon element as skeleton, is to utilize the constitutionally stable advantage of material with carbon element, can obtain the battery of long circulation life; Utilize the advantage of material with carbon element high conductivity simultaneously, can obtain the battery of high rate capability.Add nano-oxide and can not generate lithia, thereby avoided using the reduction of capacity first.Thereby the adding of nano-oxide can improve the embedding lithium current potential of material by the electronic structure that changes material, and fail safe is improved.The adding of nano-oxide can be used as the electrophilic center simultaneously and exists, thereby improves the embedding lithium capacity of material.Use the serondary lithium battery of this composite material to have good cycle characteristics, height ratio capacity, height be efficient first, high magnification characteristic and well fail safe.
Among the present invention with the complex carbon material that contains nano-oxide serondary lithium battery as negative active core-shell material, be applicable to multiple occasion, for example mobile phone, notebook computer, portable video recorder, electronic toy and cordless power tool etc. need the occasion of removable power supply, the particularly use occasion of higher energy density, as electric automobile, hybrid vehicle, robot, military affairs, fields such as aerospace.The complex carbon material that contains oxidate nano disperse phase among the present invention also can be used on other field, as catalysis, absorbing material and electron recombination material etc.
Description of drawings
Fig. 1 is the structural representation of used lithium button simulated battery in the embodiment of the invention 1, wherein stainless steel sealing nut and electrode leading-out end 1, polytetrafluoroethylene nut 2, electrode copper collector 3, the work electrode 4 that the nanometer Ag alloy/spherical pyrolyzed hard carbon composite material is an active material, porous polypropylene barrier film Celgard 2300 (soaking through electrolyte) 5, thick 0.4mm, area are 1cm 2Metal lithium sheet to electrode 6;
Fig. 2 is in the embodiment of the invention 1 to be the X-ray diffraction pattern figure of the complex carbon material of feedstock production with sucrose and boric acid;
Fig. 3 is in the embodiment of the invention 1 to be the micro-Raman scattering figure of the complex carbon material of feedstock production with sucrose and boric acid;
Fig. 4 is in the embodiment of the invention 1 being the charging and discharging curve of the complex carbon material of feedstock production with sucrose and boric acid;
Fig. 5 is the charging and discharging curve with the material with carbon element of sucrose material preparation in the comparative example 1 of the present invention.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1, use preparation method one preparation contain oxygen complex carbon material---(B 0.4O 0.6) 0.5C 0.5Composite material
(B 0.4O 0.6) 0.5Hard carbon 0.5The preparation of composite material: (1) takes by weighing 20 gram sucrose and 5 gram boric acid are put into crucible, adds and puts into Muffle furnace after 5 ml distilled waters mix, and pre-burning is 5 hours under 150 degree conditions; (2) atrament that step 1 is obtained grinds, and puts into aluminium oxide boat, and in tube furnace, logical argon shield at the uniform velocity was warming up to 900 ℃ in 5 hours, was incubated 2 hours, and the cooling back is taken out stand-by.The X-ray diffraction pattern figure of this composite material has only the peak of material with carbon element as shown in Figure 2 in the diffraction pattern, show that boron oxide is not agglomerated into piece in the material, does not have activity in X ray is surveyed.The Raman scattering figure of this composite material has only the vibration peak of carbon as shown in Figure 3 in the material, show that boron oxide does not become single phase, but exist in composite material with disperse state.
Contain of the application of oxidate nano disperse phase complex carbon material as the secondary lithium battery cathode active material, the preparation method of this electrode is as follows: with the above-mentioned oxidate nano disperse phase complex carbon material that contains, mix the formation slurry at normal temperatures and pressures with N-methyl pyrrolidone solution as the Kynoar of binding agent, evenly be coated on the Copper Foil substrate as collector the about 100 μ m of gained film thickness.With the film that obtains at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down.The percentage by weight of oven dry back composite material and Kynoar is 95: 5, and then film being cut to area is 1cm 2Thin rounded flakes investigate its chemical property as containing oxidate nano disperse phase complex carbon material electrode as the serondary lithium battery negative active core-shell material, adopts one to test button cell and study.The Experimental cell structure as shown in Figure 1, electrolyte is the lithium hexafluoro phosphate (LiPF of 1 mol 6) be dissolved in the solution of propylene carbonate, after stainless steel sealing nut 1, polytetrafluoroethylene nut 2, stainless steel spring sheet 3, work electrode 4, porous polypropylene barrier film 5 dryings, in the argon filling glove box by the Experimental cell that is assembled into shown in Figure 6.Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.Current density is 0.1mA/cm 2, the charging cut-ff voltage is 2.0V, discharge cut-off voltage is 0.00V.The charging and discharging curve of this material is seen shown in Figure 4, and the above capacity of material zero volt reaches 300mAh/g.
Embodiment 2～10, use and embodiment 1 identical method obtain nine kinds different be used for serondary lithium battery contain the oxygen complex carbon material, list in table 1
Embodiment 11, utilize that preparation method two preparation is used for serondary lithium battery contain oxygen complex carbon material---(Si 0.33O 0.67) 0.2C 0.8Composite material
(Si 0.33O 0.67) 0.2C 0.8The preparation of composite material: getting 10 gram silicone contents is that 20% aminomethyl phenyl silane is put into alumina crucible, and 5 degree under the condition of argon shield/minute be warming up to 800 degree are incubated natural cooling after 2 hours, take out stand-by.
With the method that contains employing of oxidate nano disperse phase complex carbon material and embodiment one in the present embodiment, the preparation electrode also is assembled into Experimental cell.Electrolyte is that the lithium hexafluoro phosphate of 1 mol is dissolved in 1: 1 vinyl carbonate of volume ratio and dimethyl carbonate mixed solution.Other material in the battery, structure, assembling and method of testing are with embodiment 1.
Embodiment 12～20, use and embodiment 11 identical methods obtain nine kinds different be used for serondary lithium battery contain the oxygen complex carbon material, test condition is listed in table 1 with embodiment 1
Embodiment 21～40, use and embodiment 1 identical method obtain 19 kinds different be used for serondary lithium battery contain the oxygen complex carbon material, test condition is listed in table 1 with embodiment 1
Embodiment 41, utilize that preparation method three preparation is used for serondary lithium battery contain oxygen complex carbon material---(Li 0.67O 0.33) 0.5C 0.5Composite material
(Li 0.67O 0.33) 0.5C 0.5The preparation of composite material: utilize the energetic particle beam bombardment to support by the arm the graphite target of 50% lithia, allow graphite and lithia deposit then, base reservoir temperature 50 degree, sedimentation time 150 minutes at substrate surface.It is stand-by that the gained sample takes out grinding.
The oxidate nano disperse phase complex carbon material that contains in the present embodiment is adopted the method identical with embodiment 1, prepare electrode and also be assembled into Experimental cell.Other material in the battery, structure, assembling and method of testing are with embodiment 2.
Embodiment 42～50, use and embodiment 41 identical methods obtain nine kinds different be used for serondary lithium battery contain the oxygen complex carbon material, test condition is listed in table 1 with embodiment 1
Embodiment 51, utilize that preparation method four preparation is used for serondary lithium battery contain oxygen complex carbon material---(Li 0.67O 0.33) 0.7C 0.3Composite material
(Li 0.67O 0.33) 0.7C 0.3The preparation of composite material: the crucible that lithium hydroxide will be housed is heated to 800 degree, argon gas with 20 ml/min flow velocitys is brought volatile matter in the cvd furnace into, with the argon gas of 10 ml/min flow velocitys toluene gas is brought in the cvd furnace into temperature 700 degree in the cvd furnace, sedimentation time 1 hour simultaneously.Product takes out stand-by.
The oxidate nano disperse phase complex carbon material that contains in the present embodiment is adopted the method identical with embodiment 1, prepare electrode and also be assembled into Experimental cell.Other material in the battery, structure, assembling and method of testing are with embodiment 2.
Embodiment 52～60, use and embodiment 51 identical methods obtain nine kinds different be used for serondary lithium battery contain the oxygen complex carbon material, test condition is listed in table 1 with embodiment 1
Embodiment 61, utilize that preparation method five preparation is used for serondary lithium battery contain oxygen complex carbon material---(Mg 0.5O 0.5) 0.1C 0.9Composite material
(Mg 0.5O 0.5) 0.1C 0.9The preparation of composite material: take by weighing 2 gram magnesium oxide pressed powders, take by weighing 18 gram graphite powders simultaneously, put into volume and be 50 milliliters ball grinder, ball milling is 20 hours in high energy ball mill, 500 rev/mins of rotational speed of ball-mill.Product take out stand-by.
The oxidate nano disperse phase complex carbon material that contains in the present embodiment is adopted the method identical with embodiment 1, prepare electrode and also be assembled into Experimental cell.Other material in the battery, structure, assembling and method of testing are with embodiment 2.Embodiment 62～70, use and embodiment 61 identical methods obtain nine kinds different be used for serondary lithium battery contain the oxygen complex carbon material, test condition is listed in table 1 with embodiment 1
Embodiment 71, utilize that preparation method six preparation is used for serondary lithium battery contain oxygen complex carbon material---(Si 0.33O 0.67) 0.85C 0.15Composite material
(Si 0.33O 0.67) 0.85C 0.15The preparation of composite material: at first take by weighing 17 gram silica nanometer powder (average grain diameter 25 nanometers) and put into aluminium oxide boat; in being connected with the tube furnace of argon shield with 3 degree/minute be warming up to, 800 degree; be incubated 2 hours; logical acetylene gas (100 ml/min) in insulating process; change natural cooling behind the logical argon gas then, take out stand-by.
The oxidate nano disperse phase complex carbon material that contains in the present embodiment is adopted the method identical with embodiment 1, prepare electrode and also be assembled into Experimental cell.Other material in the battery, structure, assembling and method of testing are with embodiment 2.Embodiment 72～73, use and embodiment 71 identical methods obtain two kinds different be used for serondary lithium battery contain the oxygen complex carbon material, test condition is listed in table 1 with embodiment 1
Embodiment 74, utilize that preparation method seven preparation is used for serondary lithium battery contain oxygen complex carbon material---O 0.1C 0.9Composite material
O 0.1C 0.9The preparation of composite material: take by weighing 20 gram graphite powders under the argon shield condition with 5 degree/minute be warming up to 1000 degree, change in argon-mixed 15 minutes of the logical oxygen that contains oxygen 1%, gain argon gas, natural cooling takes out stand-by.
The oxidate nano disperse phase complex carbon material that contains in the present embodiment is adopted the method identical with embodiment 1, prepare electrode and also be assembled into Experimental cell.Other material in the battery, structure, assembling and method of testing are with embodiment 2.
Embodiment 75～77, use and embodiment 74 identical methods obtain two kinds different be used for serondary lithium battery contain the oxygen complex carbon material, test condition is listed in table 1 with embodiment 1
Embodiment 78～82, use and embodiment 11 identical methods obtain three kinds different be used for serondary lithium battery contain the oxygen complex carbon material, test condition is listed in table 1 with embodiment 1
Comparative example 1
Take by weighing 20 gram sucrose and put into crucible, add and put into Muffle furnace after 5 ml distilled waters mix, pre-burning is 5 hours under 150 degree conditions; (2) atrament that step 1 is obtained grinds, and puts into aluminium oxide boat, and in tube furnace, logical argon shield at the uniform velocity was warming up to 900 ℃ in 5 hours, was incubated 2 hours, and the cooling back is taken out stand-by.
Material with carbon element in this comparative example is adopted the method identical with embodiment one, prepare electrode and also be assembled into experiment.Other material in the battery, structure, assembling and method of testing are with embodiment one.The charging and discharging curve of this material is seen shown in Figure 5, and the above reversible capacity of zero volt at the hard carbon material that does not add oxidate nano disperse phase has only 230mAh/g as can be seen.
Experimental cell among table 1, the embodiment 1～82 discharge and recharge data
The embodiment numbering The preparation method Carbon matrix precursor Form The nano oxide dispersion phase size The composite material size Reversible capacity (mAh/g) Efficient % first Cyclicity
????1 One Sucrose ????(B 0.4O 0.6) 0.5C0.5 ???8nm ???5um ???298 ???85 Good
????2 One Glucose ????(H 0.1P 0.2O 0.7) 0.1C 0.9 ??10nm ???1um ???300 ???5 Good
????3 One Fructose ????(S 0.33O 0.67) 0.25C 0.75 ??25nm ???50um ???280 ???80 Good
????4 One Raffinose ????(N 0.4O 0.6) 0.15C 0.85 ??50nm ???10um ???340 ???81 Good
????5 One Sucrose ????(Al 0.4O 0.6) 0.3C 0.7 ??80nm ???15um ???450 ???82 Good
????6 One Polyvinyl alcohol ????(Be 0.5O 0.5) 0.005C 0.995 ??50nm ???8um ???400 ???89 Good
????7 One Starch ????(Na 0.67O 0.33) 0.05C 0.95 ??20nm ???4um ???310 ???90 Good
????8 One Poly furfuryl alcohol ????(K 0.67O 0.33) 0.02C 0.98 ??45nm ???40um ???400 ???91 Good
????9 One Poly-furfural ????(Ca 0.5O 0.5) 0.004C 0.996 ??90nm ???0.1um ???380 ???87 Good
????10 One Phenolic resins ????(V 0.33O 0.67) 0.4C 0.6 ??20nm ???30um ???360 ???69 Good
????11 Two Silane ????(Si 0.33O 0.67) 0.2C 0.8 ??0.5nm ???5um ???600 ???70 Good
????12 Two Silane ????(Si 0.33O 0.67) 0.9C 0.1 ??0.3nm ???0.1um ???800 ???75 Good
????13 Two Phthalocyanine ????(Li 0.67O 0.33) 0.3C 0.7 ??0.3nm ???0.01um ???500 ???68 Good
????14 Two Phthalocyanine ????(Al 0.4O 0.6) 0.5C 0.5 ??0.5nm ???0.05um ???450 ???80 Good
????15 Two Phthalocyanine ????(Ca 0.5O 0.5) 0.3C 0.7 ??0.3nm ???50um ???350 ???92 Good
????16 Two Phthalocyanine ????(Ti 0.33O 0.67) 0.4C 0.6 ??0.2nm ???0.001um ???650 ???85 Good
????17 Two Phthalocyanine ????(Ba 0.5O 0.5) 0.2C 0.8 ????1nm ???0.02um ???700 ???84 Good
????18 Two Borine ????(B 0.4O 0.6) 0.1C 0.9 ???10nm ???10um ???420 ???82 Good
????19 Two Borine ????(B 0.4O 0.6) 0.2C 0.8 ????5nm ???30um ???300 ???78 Good
????20 Two Sulfo group alkane ????(S 0.4O 0.6) 0.01C 0.99 ????8nm ???25um ???320 ???78 Good
????21 One Graphitization mesophase carbon bead ????(B 0.4O 0.6) 0.2C 0.8 ????2nm ???5um ???400 ???78 Good
????22 One Petroleum coke ????(B 0.4O 0.6) 0.001C 0.999 ????1nm ???0.1um ???400 ???82 Good
????23 One The needle-like coke ????(Sc 0.4O 0.6) 0.02C 0.98 ????3nm ??0.2um ??300 ???86 Good
????24 One The needle-like coke ????(Y 0.4O 0.6) 0.25C 0.75 ????5nm ??0.6um ??300 ???89 Good
????25 One Micropore hard carbon ball ????(Zr 0.33O 0.67) 0.3C 0.7 ????5nm ??10um ??600 ???78 Good
????26 One Carbon fiber ????(Mo 0.25O 0.75) 0.2C 0.8 ????8nm ???5um ??380 ???75 Good
????27 One Carbon molecular sieve ????(W 0.25O 0.75) 0.5C 0.5 ????50nm ??15um ??800 ???74 Good
????28 One Native graphite ????(Cr 0.25O 0.75) 0.45C 0.55 ????2nm ??1um ??730 ???79 Good
????29 One Native graphite ????(Rb 0.5O 0.5) 0.75C 0.25 ????1nm ??2um ??380 ???71 Good
????30 One Active carbon ????(Sr 0.5O 0.5) 0.25C 0.75 ????0.5nm ??5um ??510 ???69 Good
????31 One Active carbon ????(Ce 0.33O 0.67) 0.1C 0.9 ????1nm ??5um ??550 ???69 Good
????32 One Active carbon ????(Ce 0.5O 0.5) 0.11C 0.89 ????1.5nm ??10um ??1000 ???68 Good
????33 One Active carbon ????(Nb 0.5O 0.5) 0.81C 0.19 ????10nm ??200um ??1200 ???75 Good
????34 One Active carbon ????(Nb 0.33O 0.67) 0.11C 0.99 ????2nm ??10um ??1200 ???72 Good
????35 One Carbon molecular sieve ????(Si 0.33O 0.67) 0.1C 0.9 ????0.5nm ??15um ??2100 ???79 Good
????36 One Carbon molecular sieve ????(Pr 0.33O 0.67) 0.2C 0.8 ????0.2nm ??0.1um ??1800 ???80 Good
????37 One Carbon molecular sieve ????(Sm 0.33O 0.67) 0.4C 0.6 ????2nm ??0.1um ??2200 ???84 Good
????38 One The porous hard carbon ????(Si 0.33O 0.67) 0.5C 0.5 ????50nm ??2um ??870 ???75 Good
????39 One Expanded graphite ????(Eu 0.5O 0.55) 0.2C 0.8 ????15nm ??20um ??410 ???87 Good
????40 One Expanded graphite ????(Gd 0.5O 0.5) 0.12C 0.88 ????5nm ??10um ??395 ???78 Good
????41 Three Graphite ????(Li 0.67O 0.33) 0.5C 0.5 ????0.3nm ??1um ??380 ???90 Good
????42 Three Graphite ????(V 0.33O 0.67) 0.5C 0.5 ????0.8nm ??5um ??395 ???93 Good
????43 Three Graphite ????(Cr 0.25O 0.75) 0.45C 0.55 ????1.0nm ??20um ??430 ???96 Good
????44 Three Graphite ????(Tm 0.5O 0.5) 0.35C 0.65 ????0.3nm ??15um ??430 ???88 Good
????45 Three Graphite ????(Tb 0.33O 0.67) 0.25C 0.75 ????0.5nm ??7um ??510 ???87 Good
????46 Three Graphite ????(Dy 0.5O 0.5) 0.15C 0.85 ????1.5nm ??50um ??480 ???85 Good
????47 Three Hard carbon ????(Er 0.5O 0.5) 0.5C 0.5 ????2.0nm ??20um ??550 ???75 Good
????48 Three Hard carbon ????(Ho 0.5O 0.5) 0.2C 0.8 ????5.0nm ??40um ??600 ???84 Good
????49 Three Hard carbon ????(Yb 0.3O 0.7) 0.85C 0.15 ????20nm ??5um ??440 ???86 Good
????50 Three Hard carbon ????(Lu 0.5O 0.5) 0.65C 0.35 ????20nm ??6um ??445 ???75 Good
????51 Four Toluene ????(Li 0.67O 0.33) 0.7C 0.3 ??10nm ??0.1um ??200 ???75 Good
????52 Four Ethene ????(Li 0.67O 0.33) 0.5C 0.5 ???7nm ??0.2um ??245 ???65 Good
????53 Four Methane ????(Li 0.67O 0.33) 0.2C 0.8 ???8nm ??1um ??300 ???75 Good
????54 Four Ethane ????(K 0.67O 0.33) 0.15C 0.85 ??12nm ??3um ??500 ???72 Good
????55 Four Dimethylbenzene ????(K 0.67O 0.33) 0.35C 0.65 ??15nm ??10um ??555 ???84 Good
????56 Four Phenol ????(Y 0.67O 0.33) 0.75C 0.25 ??30nm ??20um ??625 ???88 Good
????57 Four Benzene ????(Ti 0.67O 0.33) 0.7C 0.3 ??50nm ??5um ??200 ???86 Good
????58 Four Acetylene ????(V 0.67O 0.33) 0.15C 0.85 ??80nm ??40um ??350 ???87 Good
????59 Four Propylene ????(Na 0.67O 0.33) 0.22C 0.78 ???2nm ??3.5um ??200 ???84 Good
????60 Four Cyclohexane ????(K 0.67O 0.33) 0.5C 0.5 ???30nm ??1um ??200 ???89 Good
????61 Five Graphite powder ????(Mg 0.5O 0.5) 0.1C 0.9 ??100nm ??15um ??350 ???91 Good
????62 Five Graphite powder ????(Mg 0.5O 0.5) 0.4C 0.6 ????1nm ??20um ??350 ???83 Good
????63 Five Graphite powder ????(Al 0.4O 0.6) 0.8C 0.2 ????9nm ??5um ??400 ???93 Good
????64 Five Hard carbon ????(Al 0.4O 0.6) 0.25C 0.75 ????5nm ??3um ??450 ???95 Good
????65 Five Delanium ????(Si 0.5O 0.5) 0.9C 0.1 ????1nm ??28um ??440 ???72 Good
????66 Five Acetylene black ????(Ca 0.5O 0.5) 0.7C 0.3 ????3nm ??1um ??260 ???79 Good
????67 Five The charcoal ash ????(Tm 0.5O 0.5) 0.2C 0.8 ????5nm ??0.5um ??200 ???77 Good
????68 Five Acetylene black ????(Ca 0.5O 0.5) 0.9C 0.1 ????3nm ??3um ??220 ???80 Good
????69 Five Acetylene black ????(Mg 0.5O 0.5) 0.4C 0.6 ????4nm ??0.5um ??240 ???81 Good
????70 Five Flue dust ??(Al 0.25Si 0.25O 0.5) 0.8C 0.2 ????9nm ??1um ??300 ???88 Good
????71 Six Acetylene ??(Si 0.33O 0.67) 0.85C 0.15 ??0.3nm ??9um ??400 ???74 Good
????72 Six Ethene ??(Al 0.4O 0.6) 0.05C 0.95 ??0.9nm ??5um ??385 ???78 Good
????73 Six Between trimethylbenzene ??(Mg 0.45O 0.55) 0.75C 0.25 ??0.4nm ??7um ??150 ???81 Good
????74 Seven Graphite powder ?????????O 0.1C 0.9 ??005nm ??500um ??300 ???80 Good
????75 Seven Hard carbon ?????????O 0.15C 0.85 ??0.3nm ??15um ??400 ???80 Good
????76 Seven Petroleum coke ?????????O 0.2C 0.8 ??0.1nm ??14um ??450 ???79 Good
????77 Seven Hard carbon ????????O 0.15C 0.8H 0.05 ??0.1nm ???5um ??400 ???80 Good
????78 Two The banyan root ????(Si 0.3Al 0.08O 0.62) 0.001C 0.999 ??0.5nm ??10um ??800 ???86 Good
????79 Two Bark (Si 0.4Al 0.06O 0.52) 0.05C 0.95 ????0.25nm ??20um ???700 ???73 Good
????80 Two Mao bamboon (Si 0.3Al 0.18O 0.52) 0.01C 0.99 ????0.2nm ??50um ???650 ???73 Good
????81 Two Grass roots (Si 0.35Mg 0.28O 0.37) 0.002C 0.998 ??0.1nm ??100um ???450 ???85 Good
????82 Two Grass roots (Si 0.3Al 0.18O 0.52) 0.01C 0.98H 0.01 0.2nm ??15um ???700 ???80 Good

Claims (11)

1, a kind of be used for serondary lithium battery contain the oxygen complex carbon material, comprising:
1) nano-oxide;
With 2) material with carbon element;
It is 0.1～70wt% that nano-oxide accounts for the percentage by weight that contains the oxygen complex carbon material;
The expression formula of described nano-oxide is M 1 X1M 2 X2M n XnO x, M wherein 1, M 2M nRepresent different elements, be selected from Li, Be, N, Na, Mg, B, Al, Si, P, S, Se, Te, K, Ca in the major element, or the Sc of transition metal, Ti, V, Cr, Mn, Rb, Sr, Y, Zr, Nb, Mo, W, Ta, Hf, La, Ba, Cs, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Subscript x1, x2 ... xn, x represent the molar percentage of different element atoms, and x1+x2+ ... + xn+x=1;
Described material with carbon element comprises native graphite, graphitization or not graphitization mesocarbon bead, needle coke, petroleum coke, the hard charcoal ball of micropore, carbon fiber, low temperature pyrogenation carbon, carbon black, active carbon, porous carbon, carbon molecular sieve;
The described average-size that contains the oxygen complex carbon material that is used for serondary lithium battery is 1nm～500um;
The average-size of described nano-oxide is 0.1nm～100nm.
2, by claim 1 described be used for serondary lithium battery contain the oxygen complex carbon material, it is characterized in that: described nano-oxide is B 0.4O 0.6, H 0.1P 0.2O 0.7, S 0.33O 0.67, N 0.4O 0.6, Al 0.4O 0.6, Na 0.67O 0.33, Be 0.5O 0.5, K 0.67O 0.33, Ca 0.5O 0.5, V 0.33O 0.67, Si 0.33O 0.67, Si 0.33O 0.67, Ti 0.33O 0.67, Sc 0.4O 0.6, Y 0.4O 0.6, Zr 0.33O 0.67, Mo 0.25O 0.75, W 0.25O 0.75, Cr 0.25O 0.75, Sr 0.5O 0.5, Ce 0.33O 0.67, Nb 0.5O 0.5, Al 0.25Si 0.25O 0.5, Si 0.3Al 0.08O 0.62, Si 0.35Mg 0.28O 0.37
3, by claim 1 described be used for serondary lithium battery contain the oxygen complex carbon material, it is characterized in that: described be used for serondary lithium battery contain the oxygen complex carbon material, also comprise: 3) hydrogen; Hydrogen account for contain the oxygen complex carbon material percentage by weight less than 5wt%.
4, the described preparation method who contains the oxygen complex carbon material who is used for serondary lithium battery of a kind of claim 1 adds the material that oxide maybe can be decomposed to form oxide in the predecessor of carbon, carbonization obtains composite material then.
5, the described preparation method who contains the oxygen complex carbon material who is used for serondary lithium battery of a kind of claim 1, utilization contains the hetero-atom organic carbon and obtains composite material.
6, the described preparation method who contains the oxygen complex carbon material who is used for serondary lithium battery of a kind of claim 1 uses material with carbon element and oxide to be target, deposits in substrate by sputtering method and obtains composite material.
7, the described preparation method who contains the oxygen complex carbon material who is used for serondary lithium battery of a kind of claim 1 utilizes to be added with the method for carbon matrix precursor by chemical vapour deposition (CVD) that oxide maybe can be decomposed to form the material of oxide and to obtain composite material.
8, the described preparation method who contains the oxygen complex carbon material who is used for serondary lithium battery of a kind of claim 1 utilizes high-energy ball milling that the material that material with carbon element and oxide maybe can be decomposed to form oxide is carried out obtaining after the mechanical mixture.
9, the described preparation method who contains the oxygen complex carbon material who is used for serondary lithium battery of a kind of claim 1 uses the oxide of nanoscale to obtain after the surface carbon coating at low temperatures.
10, the described preparation method who contains the oxygen complex carbon material who is used for serondary lithium battery of a kind of claim 1 obtains material with carbon element oxidation in the oxidizing atmosphere of gentleness.
11, a kind of claim 1 described be used for serondary lithium battery contain the purposes of oxygen complex carbon material as the secondary lithium battery cathode active material.
CNA031600506A 2003-09-26 2003-09-26 Oxygen-contg composite carbon material for secondary lithium cell, its prepn process and usage Pending CN1601786A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101533907B (en) * 2009-04-14 2010-10-27 北京科技大学 Method for preparing silicon-based anode material of lithium-ion battery
CN102005569A (en) * 2009-08-28 2011-04-06 上海宝钢化工有限公司 Composite cathode material for lithium ion battery and preparation method thereof
CN102185142A (en) * 2011-04-08 2011-09-14 厦门大学 Composite carbon cathode material for lithium ion battery and preparation method thereof
CN105355884A (en) * 2015-11-25 2016-02-24 上海理工大学 High-specific-capacity lithium ion battery electrode material and preparation method thereof
CN106241964A (en) * 2016-08-22 2016-12-21 江苏金点环保科技有限公司 Bipolar membrane electro-catalysis processing means
CN106311297A (en) * 2016-08-22 2017-01-11 江苏金点环保科技有限公司 Columnar carbon electrocatalyst improving method
CN110676443A (en) * 2019-08-23 2020-01-10 广东工业大学 Nitrogen-doped hollow carbon sphere with phthalocyanine as precursor and preparation method and application thereof
CN111446428A (en) * 2020-03-23 2020-07-24 珠海冠宇电池股份有限公司 Lithium negative electrode material and application thereof
CN116314603A (en) * 2023-05-25 2023-06-23 宁德新能源科技有限公司 Negative electrode plate, electrochemical device and electronic device

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101533907B (en) * 2009-04-14 2010-10-27 北京科技大学 Method for preparing silicon-based anode material of lithium-ion battery
CN102005569A (en) * 2009-08-28 2011-04-06 上海宝钢化工有限公司 Composite cathode material for lithium ion battery and preparation method thereof
CN102185142A (en) * 2011-04-08 2011-09-14 厦门大学 Composite carbon cathode material for lithium ion battery and preparation method thereof
CN105355884A (en) * 2015-11-25 2016-02-24 上海理工大学 High-specific-capacity lithium ion battery electrode material and preparation method thereof
CN106241964A (en) * 2016-08-22 2016-12-21 江苏金点环保科技有限公司 Bipolar membrane electro-catalysis processing means
CN106311297A (en) * 2016-08-22 2017-01-11 江苏金点环保科技有限公司 Columnar carbon electrocatalyst improving method
CN110676443A (en) * 2019-08-23 2020-01-10 广东工业大学 Nitrogen-doped hollow carbon sphere with phthalocyanine as precursor and preparation method and application thereof
CN111446428A (en) * 2020-03-23 2020-07-24 珠海冠宇电池股份有限公司 Lithium negative electrode material and application thereof
CN116314603A (en) * 2023-05-25 2023-06-23 宁德新能源科技有限公司 Negative electrode plate, electrochemical device and electronic device
CN116314603B (en) * 2023-05-25 2023-09-01 宁德新能源科技有限公司 Negative electrode plate, electrochemical device and electronic device

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