CN1773752A - Chromium-base negative electrode active material for secondary lithium battery - Google Patents

Chromium-base negative electrode active material for secondary lithium battery Download PDF

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CN1773752A
CN1773752A CNA2004100907000A CN200410090700A CN1773752A CN 1773752 A CN1773752 A CN 1773752A CN A2004100907000 A CNA2004100907000 A CN A2004100907000A CN 200410090700 A CN200410090700 A CN 200410090700A CN 1773752 A CN1773752 A CN 1773752A
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lithium battery
active material
chromium
negative electrode
electrode active
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CN100369301C (en
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胡进
李泓
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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A Cr based negative electrode active material used on secondary lithium cell is oxide Cr2-xMxO3 of transition metal Cr doped with varied atoms as 0.001 not greater than x not greater than 1.5, M being li, Ag, mg, Ni, Cu, Zn, Sn, Co, Fe, Ca, Sr, Ti, Mn, Ce, Mo or Zr, material particle diameter being 50nm to 20 micron. The said material also can include conductive additives with the amount of 1-20 wt% to said material, or can have carbon film shell on said material core, or can apply 20-98 wt % ratio to mix with existing negative electrode material for being used as negative electrode material of secondary lithium cell.

Description

A kind of chromium-base negative electrode active material that is used for serondary lithium battery
Technical field
The present invention relates to a kind of chromium-base negative electrode active material that is used for serondary lithium battery.
Background technology
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 metal serondary lithium battery negative pole 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 to 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 are meeting efflorescence gradually in the repeated charge process, it is the dimension instability, cause the variation that electrically contacts between alloy particle and the collector and between the alloy particle, cause battery performance to degenerate even lost efficacy (document [1]: A Bolahanmu, electrochemistry communication, 138 volumes, 1233 pages, 1993).
In 1980, Armand (M.Armand) proposes serondary lithium battery can adopt " rocking chair type " battery system (" lithium ion " battery afterwards was otherwise known as), be that the both positive and negative polarity active material all adopts embedding compound (intercalationcompounds), this compounds can be reversible storage and exchange lithium ion, thereby avoid using lithium metal or lithium alloy.Typical negative material such as LiWO 2And Li 6Fe 2O 3Deng, but its energy density greatly reduces.Through the effort in 10 years, in March, 1989, Japanese Sony Corporation 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 (document [2]: Bu Lunuo, electrochemistry can will, 139 volumes, 2776 pages, 1992).
From then on, serondary lithium battery begins to develop rapidly.The material with carbon element of various ways such as petroleum coke, carbon fiber, RESEARCH OF PYROCARBON, native graphite, Delanium extensively is elected to be the secondary lithium battery cathode active material.But carbon is 372mAh/g as the theoretical specific capacity of negative active core-shell material, still can not satisfy the further pursuit of people to the high-energy density secondary battery.
Have been found that some transition metal oxide, sulfide, fluoride, for example cuprous oxide and cupric oxide (Cu 2O, CuO), cobalt oxide (CoO, Co 3O 4), iron oxide (Fe 2O 3), nickel oxide (NiO), ruthenium-oxide (RuO 2), cobalt sulfide (CoS 0.89), titanium fluoride (TiF 3), vanadium fluoride (VF 3) can reversible lithium storage, and the reversible lithium storage capacity is up to 400～1000mAh/g (document [3]: P.Poizot, S.Laruelle, S.Grugeon, L.Dupont, J.M.Tarascon, Nature, 407,496 (2000); And document [4]: H.Li, G.Richter, J.Maier, Adv.Mater., 15,736 (2003)).
But show through experiment and Theoretical Calculation, the thermodynamical equilibrium current potential of these material storage lithiums generally is higher than 1.5V, because electrochemical polarization, the actual lithium current potential platform that takes off often is higher than 2 volts, these materials are as the negative material of lithium ion battery, when arranging in pairs or groups with positive electrode, the integral energy density of battery does not significantly improve.Discover in addition, the cycle performance of the transition metal oxide of having reported, sulfide, fluoride or nitride is relatively poor, mainly is that the change in volume of active material particle is bigger because the embedding lithium takes off in the lithium process, along with charge and discharge cycles, electrically contact variation gradually between the active material.And the passivating film of particle surface in cyclic process repeatedly the growth come off, this process can consume lithium, causes the battery reversible capacity to descend gradually.In addition, these transition metal oxides, first all efficiency for charge-discharges of fluoride are all less than 70%.
Show Cr through experiment and Theoretical Calculation 2O 3The thermodynamical equilibrium current potential of storage lithium is 1.08V, is lower than other transition metal oxide.Cr 2O 3As the negative material of lithium ion battery, when arranging in pairs or groups with positive electrode, the integral energy density of battery will be significantly increased.We have applied for relevant patent (CN200410030990.x).
But, Cr 2O 3The same with other transition metal oxides, it is low to exist starting efficiency, shortcomings such as cyclicity difference, and this is more relevant with its change in volume.In order to address this problem, we propose to adopt nucleocapsid structure or the vivider material that is referred to as structure on Lantern Festival to solve this problem in patent CN200410030990.x, in Lantern Festival structure, the change in volume of inner active material in charge and discharge process is subjected to the inhibition of outer shell pyrolytic carbon layer and CVD carbon-coating, and the buffering of inner conductive additive.And, even crucial part also is active material efflorescence in charge and discharge process, also can keep good electrical contact with the inner conductive additive all the time.In addition, because inner active material is wrapped up by carbon-coating, the growth of surface passivated membrane is only relevant with the carbon of outer shell, and the specific area of this layer significantly reduces owing to covered fine and close CVD carbon-coating, the benefit of bringing like this is growth and the decomposition that passivating film has been avoided on inner active material surface, the passivating film of outer surface can stable growth, and the lithium that consumes is few.Because remarkable change in volume and bigger irreversible capacity loss that inner active material causes all are able to remarkable reduction.By our a large amount of experimental results show that, the above-mentioned secondary lithium battery cathode active material that is used for structure on Lantern Festival has made full use of and has brought into play the big advantage of inner active material lithium storage content, solved the problem of change in volume, solved surface passivated membrane growth problem of unstable, so cyclicity and efficiency for charge-discharge significantly improve.
The electronic conductance of further discovering electrode material also is another key factor that influences transition metal oxide chemical property in lithium battery.In the telescopiny of lithium ion, Cr 2O 3Crystal structure is destroyed gradually, forms the nano metal Cr and the Li of indefiniteness 2The compound of O is wrapped in Cr 2O 3The surface, the electronic conductance of this compound will be higher than Cr 2O 3Body.The insertion reaction of lithium ion can very successfully carry out like this, always will be Cr 2O 3Fully till the reduction.But taking off the lithium process, situation is just in time opposite, has just begun to take off the Cr that lithium forms 2O 3Wrap in the nano metal Cr and the Li of indefiniteness 2The composite surface of O, and Cr 2O 3Electronic conductance far below unbodied nano metal Cr and Li 2The compound of O.Work as Cr 2O 3Thick take off to a certain degree the time lithium just since internal resistance can not go on too greatly.Here it is most transition metal oxides are the low and relatively poor main cause of cyclicity of efficient first.
Summary of the invention
The objective of the invention is to overcome existing secondary lithium battery cathode material cyclicity and the low defective of efficiency for charge-discharge, improve Cr thereby mix by hetero-atom 2O 3Electronic conductance to reach the chemical property that improves this class material significantly, or constitute composite material with carbon and further improve its chemical property with nucleocapsid structure, provide a kind of can be so that serondary lithium battery has the chromium-base negative electrode active material that is used for serondary lithium battery of higher charge/discharge capacity and cycle characteristics and fail safe preferably.
The objective of the invention is to realize by the following technical solutions:
The chromium-base negative electrode active material that is used for serondary lithium battery provided by the invention, it is the oxide of heteroatomic transition metal chromium of having mixed, its chemical formula is Cr 2-xM xO 3, 0.001≤x≤1.5 wherein; Hetero-atom M is Li, Ag, Mg, Ni, Cu, Zn, Sn, Co, Fe, Ca, Sr, Ti, Mn, Ce, Sn, Mo or Zr etc.; The particle diameter of material granule is 50 nanometers to 20 micron.
The chromium-base negative electrode active material that is used for serondary lithium battery provided by the invention, also comprise the oxide of transition metal chromium of above-mentioned doping and the mixture of conductive additive, described conductive additive is graphite powder, conductive black, acetylene black, metal powder, carbon nano-tube, carbon fiber or metallic fiber, wherein the particle diameter of graphite powder, conductive black, acetylene black or metal powder is 10 nanometers to 10 micron, the diameter of carbon nano-tube, carbon fiber or metallic fiber is 5～200nm, length is 10 nanometers to 10 micron, and conductive additive accounts for 1～20wt% of the total weight of material.
The chromium-base negative electrode active material that is used for serondary lithium battery provided by the invention, also be included in outside " nuclear " of mixture of the oxide of the oxide of above-mentioned transition metal chromium or transition metal chromium and conductive additive, one or more layers the carbon film or " shell " of carbon granule are arranged, its center partly account for material total weight 50～99%, shell partly account for material total weight 1～50%.Have conductive additive in the composite material of nucleocapsid structure and account for 1～20wt% of the total weight of material.
The above-mentioned chromium-base negative electrode active material that is used for serondary lithium battery provided by the invention can be directly used in this material the secondary lithium battery cathode material; Also can mix with other existing negative material (as graphite) and be used for the secondary lithium battery cathode material, wherein, the chromium-base negative electrode active material that is used for serondary lithium battery of the present invention accounts for 20～98wt% of total negative material weight.
When adopting material provided by the invention as the secondary lithium battery cathode active material, the preparation method of battery cathode adopts the preparation method who has general lithium ion battery negative now.For example, be used for the secondary lithium battery cathode active material and (its granularity is 1～1000nm as the powder body material of conductive additive with provided by the invention, comprise acetylene black, carbon black, graphite powder etc.) mechanical mixture, the weight ratio that this conductive additive accounts for total electrode material is 0～20wt%, again with general bonding agent, nmp solution as 5% Kynoar, mix at normal temperatures and pressures and make the composite material slurries, it is coated in paper tinsel as the various conductions of collector uniformly, net, porous body, on the carrier of foams or corpus fibrosum material (as Copper Foil, nickel screen, nickel foam, carbon felt etc.).The gained film thickness makes it 100～150 ℃ of oven dry down at 2～20um then, is 0.2～20Mpa/cm at pressure 2Under compress, continue to be cut into different shape by the prepared cell specification and to be negative pole 100～150 ℃ of bakings 12 hours.
The preparation method of above-mentioned negative electrode can not be confined to this technology.Also can adopt unconventional method.The way by various physics system films for example is with the Cr that mixes 2O 3(being the oxide of transition metal chromium provided by the invention) physical deposition is at the Cu as collector, Ni, Ti and stainless steel foil surface; Perhaps on this basis, plate one deck carbon more in the above, form the sandwich construction of two dimension.
The positive electrode active materials of serondary lithium battery of the present invention is the existing positive electrode that is used for serondary lithium battery, can reversibly embed and deviate from the transistion metal compound that contains lithium of lithium, and is typical in LiCoO 2, LiNiO 2, LiMn 2O 4, LiFePO 4, LiNi 1-xCo xMnO 2Deng, Li 3CrMn 0.6O 4Deng, and be not limited to this.Anodal method for making is similar to negative pole, with positive electrode active materials, conductive additive (as acetylene black), binding agent (as the cyclohexane solution of 5% Kynoar), mix to form the composite material slurries in 85: 10: 5 by weight percentage at normal temperatures and pressures, it is coated on the aluminium foil as collector uniformly, the gained film thickness is at 5～40um, 100～150 ℃ of oven dry down, be 0.2～20Mpa/cm then at pressure 2Under compress, continue after the oven dry gained film to be cut into different shape by the prepared cell specification and to be positive pole 100～150 ℃ of bakings 12 hours.
The organic electrolyte solution of serondary lithium battery of the present invention can be added one or more solvable lithium salts by the mixed solvent that a kind of organic solvent or several organic solvent are formed and form.Typical organic solvent is vinyl carbonate (EC:ethylene carbonate) for example, propylene carbonate (PC:propylene carbonate), diethyl carbonate (DEC:diethylcarbonate), dimethyl carbonate (DME:dimethyl carbonate), ethyl-methyl carbonic ester (EMC:ethylmethyl carbonate), dimethoxy-ethane (DME:dimethoxy-ethane) etc., typical solvable lithium salts such as LiClO 4, LiBF 4, LiPF 6, LiCF 3SO 3, LiAsF 6Deng.Typical system such as 1M LiPF 6(EC-DEC volume ratio 1: 1), 1M LiPF 6(EC-DMC volume ratio 3: 7) etc. can also add various functional form additives in above-mentioned electrolyte, biphenyl for example, vinyl carbonic ester (VEC) etc.The selection of electrolyte also can be not limited to this.
The polymer dielectric of serondary lithium battery of the present invention adopts existing serondary lithium battery polymer dielectric, as polyethylene nitrile, LiClO 4, propylene carbonate and vinyl carbonate be with weight ratio 20: 5: 45: 30 mixtures of forming, or the mixture of the copolymer of Kynoar and hexafluoropropylene and lithium hexafluoro phosphate, and be not limited to this.
The barrier film that the barrier film of serondary lithium battery of the present invention is used for existing general serondary lithium battery, as the porous polypropylene barrier film, nonwoven fabrics, and be not limited to this.
The invention provides a kind of serondary lithium battery, its basic structure contains the positive pole of the compound of lithium as positive electrode active materials by containing the negative pole of material provided by the invention as negative active core-shell material, organic electrolyte solution or polymer dielectric, barrier film, collector, battery case, compositions such as lead-in wire.Wherein, separate by the barrier film that has soaked organic electrolyte solution or by polymer dielectric between positive pole and the negative pole, positive pole is burn-on respectively to go between with an end of negative pole and is linked to each other with the battery case two ends of mutually insulated.The profile of this serondary lithium battery can make button (individual layer) respectively, column type (multilaminate coiled), and square (multilayer folding), chewing gum type (multilayer folding) etc., and be not limited to this.
When material provided by the invention was used for the secondary lithium battery cathode material, it was very high to have a reversible capacity, and cyclicity is good, and the high advantage of efficiency for charge-discharge.In addition, as previously mentioned, the existing negative material of material provided by the invention and other (as graphite) is mixed when being used for the secondary lithium battery cathode material, also can improve the electrochemical properties of this mixing negative material.The atom doped Cr of a kind of Mg for example provided by the invention 2O 3The reversible capacity of negative material can reach 850mAh/g, is the graphite of 300mAh/g with itself and lithium storage content, and the reversible capacity of this composite material can reach 700mAh/g when mixed proportion was (7: 3); Lithium storage content apparently higher than graphite.
Serondary lithium battery of the present invention is applicable to that various mobile electronic devices maybe need the equipment of mobile driven by energy, mobile phone for example, notebook computer, portable video recorder, electronic toy, electric tool, electric automobile, hybrid vehicle, fields such as electric topedo, and be not limited to this.
Compare with the negative material of existing battery, the advantage that is used for the material of serondary lithium battery negative pole provided by the invention is: the present invention has adopted high power capacity, the high hetero-atom doping Cr that conducts electricity 2O 3Material or have nucleocapsid structure use the hetero-atom doping Cr of high power capacity, high conduction 2O 3Be the negative material of core active material, thereby during as secondary lithium battery cathode, it is low to have a current potential of discharging and recharging, the reversible capacity height, and cyclicity is good, and is safe and reliable, the high remarkable advantage of first all coulombic efficiencies.
Description of drawings
Fig. 1 is the charging and discharging curve of the embodiment of the invention 1 simulated battery;
Fig. 2 is the cyclicity curve of the embodiment of the invention 1 simulated battery;
Fig. 3 is the charging and discharging curve of the embodiment of the invention 2 simulated batteries;
Fig. 4 is the cyclicity curve of the embodiment of the invention 2 simulated batteries;
Fig. 5 is the charging and discharging curve of the embodiment of the invention 35 simulated batteries;
Fig. 6 is the cyclicity curve of the embodiment of the invention 35 simulated batteries;
Fig. 7 is the charging and discharging curve of the embodiment of the invention 37 simulated batteries;
Fig. 8 is the cyclicity curve of the embodiment of the invention 37 simulated batteries.
Embodiment
Embodiment 1, use liquid phase method prepare the negative active core-shell material 1 of the chromium oxide of Li doping
With a certain amount of CrCl 3Be made into the aqueous solution of 1M with lithium nitrate by the stoichiometric proportion shown in the table 1, water-bath is heated to 50 ℃, under intensively stirred situation ammoniacal liquor is added drop-wise in the above-mentioned aqueous solution, and control pH value is about 9.0.With deionized water isolated by filtration 5 times of resulting sediment, under 100 ℃, dried then through 12 hours.With the pre-burning 5 hours in 300 ℃ of following air atmosphere in Muffle furnace of the presoma after the oven dry.Take out ball milling, compressing tablet.Calcined 6 hours down at 500 ℃, cool to room temperature obtains a series of end products that are used for secondary lithium battery cathode active material 1 of the present invention again, and its average grain diameter is 50 nanometers.
In order to study the chemical property of serondary lithium battery of the present invention, adopt an Experimental cell to study.Experimental cell is at H 2Assemble in the argon filling glove box of O content＜1.0ppm.
The electrolyte of Experimental cell is 1M LiPF 6Be dissolved in the mixed solvent of vinyl carbonate and dimethyl carbonate (volume ratio is 1: 1).
The preparation of the negative pole of Experimental cell: with above-mentioned negative active core-shell material 1 respectively with conductive black, the cyclohexane solution of 5%PVDF (Kynoar) mixes formation slurry (weight ratio of drying the latter two is 90: 5: 5) at normal temperatures and pressures, evenly be coated on the Copper Foil substrate as the negative pole coating, obtain about 2～50 microns film of thickness; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down, then film being cut to area is 1cm 2Thin rounded flakes as the negative pole of Experimental cell.
The preparation of the positive pole of Experimental cell: with active material powder and conductive black, the cyclohexane solution of 5%PVDF mixes formation slurry (weight ratio after three's oven dry is 85: 10: 5), evenly be coated on the aluminum substrates as the negative pole coating, obtain thickness and be 5～40 microns film; With this film at 150 ℃ down after the oven dry, at 20Kg/cm 2Under compress, continue 150 ℃ of oven dry 12 hours down, after this film is cut to area is 1cm 2Thin rounded flakes as the positive pole of Experimental cell.
With other basic building block except that electrolyte or solid electrolyte of Experimental cell, in the argon filling glove box, be assembled into Experimental cell according to a conventional method as dryings such as negative pole, positive pole, barrier film, collector, battery case, lead-in wire back.
Use is subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles to test, and the current density of test is 0.4mA/cm 2, discharge cut-off voltage is 0V, and the charging cut-ff voltage is 3.0V, and test result is listed in table 1.
Use is by Li doping Cr of the present invention 2O 3The simulated battery of electrode slice that coats and lithium assembling is studied Li doping Cr of the present invention 2O 3Negative material is with respect to the discharge characteristics of lithium metal, and the negative pole of simulated battery is a metallic lithium foil, and the current density of charge and discharge cycles test is 0.4mA/cm 2, discharge cut-off voltage is 0V, the charging cut-ff voltage is 3V.The charging and discharging curve of simulated battery as shown in Figure 1, the cyclicity curve of simulated battery as shown in Figure 2, test result is listed in table 1 chemical property one hurdle.
Embodiment 2, use pyrolysismethod prepare chromium oxide/carbon composite material of core-shell structure 2 that Li mixes
(1) product 1 with preparation among the embodiment 1 mixes by 10: 1 weight ratio with carbon black (average grain diameter is 40 nanometers) as conductive additive, and mechanical ball milling (rotating speed is 500 rev/mins, 6 hours) obtains inner composite particles; (2) should the inside composite particles and sucrose by 1: 1 weight ratio machinery mix grinding (rotating speed is 150 rev/mins, 1 hour), obtain finely dispersed mixture; (3) with the pyrolysis under high pure nitrogen of this mixture, the step of pyrolysis is: earlier be warmed up to 400 ℃ with 4 hours from room temperature, be warmed up to 700 ℃ with 10 hours from 400 ℃ again, then at 700 ℃ of constant temperature after 12 hours, drop to room temperature with 2 hours at last, obtained coating the inside composite particles of pyrolytic carbon layer; This composite particles is mixed (the 20g composite particles is mixed in the 80ml ethanol) wet-milling 2 hours (rotating speed is 300 rev/mins) with ethanol, take out the back drying and remove ethanol; (4) (volume ratio is 1: 4 under the mist that contains toluene and high pure nitrogen, flow is 200ml/ minute, the tube furnace volume is 0.02 cubic metre), the 800 ℃ of pyrolysis in tube furnace of this composite particles (were raised to 800 ℃ with 5 hours from room temperature earlier, 800 ℃ of constant temperature 2 hours, again with dropping to room temperature in 2 hours), obtain a series of secondary lithium battery cathode active materials 2 that are used for of the present invention, this negative active core-shell material has nucleocapsid structure, outside average diameter is 20 microns, and the Cr that Li mixes is contained in its inside 2O 3With the transition metal oxide composite particles that conductive black is formed, its outside has coated the carbon granule layer from the sucrose pyrolysis, and outermost layer has coated and utilized the carbon-coating of CVD from the toluene pyrolysis, and the weight ratio of its each several part is listed in table 2.
The preparation of the negative pole of Experimental cell, anodal preparation, Experimental cell assembling and method of testing be with embodiment 1, the charging and discharging curve of simulated battery as shown in Figure 3, the cyclicity curve of simulated battery as shown in Figure 4, test result is listed in table 2 chemical property one hurdle.
Embodiment 3, use liquid phase method prepare the negative active core-shell material 3 of the chromium oxide of Ag doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 3 of the chromium oxide of Ag doping with silver nitrate, calcine 12 hours down at 800 ℃ after the presoma pre-burning after oven dry, all the other parameters are with embodiment 1, obtain a series of end products that are used for secondary lithium battery cathode active material 3 of the present invention, average grain diameter is 200 nanometers.
Embodiment 4, use pyrolysismethod to prepare the composite material of core-shell structure 4 of the formation of chromium oxide/carbon that Ag mixes
(1) product 3 with preparation among the embodiment 3 mixes by 10: 1 weight ratio with the acetylene black (average grain diameter is 10 nanometers) as conductive additive, and mechanical ball milling (rotating speed is 500 rev/mins, 6 hours) obtains inner composite particles; Press step among the embodiment 2 (2)～(4) then and handle, obtain a series of secondary lithium battery cathode active materials 4 that are used for of the present invention, this negative active core-shell material has nucleocapsid structure, and outside average diameter is 10 microns, and the Cr that Ag mixes is contained in its inside 2O 3With the transition metal oxide composite particles that conductive black is formed, its outside has coated the carbon granule layer from the sucrose pyrolysis, and outermost layer has coated and utilized the carbon-coating of CVD from the toluene pyrolysis, and the weight ratio of its each several part is listed in table 2.
Embodiment 5, use liquid phase method legal system are equipped with the negative active core-shell material 5 of the chromium oxide of Mg doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 5 of the chromium oxide of Mg doping with magnesium chloride, calcine 24 hours down at 800 ℃ after the presoma pre-burning after oven dry, all the other parameters are with embodiment 1, obtain a series of end products that are used for secondary lithium battery cathode active material 5 of the present invention, average grain diameter is 10 microns.
Embodiment 6, use pyrolysismethod to prepare the composite material of core-shell structure 6 of the formation of chromium oxide/carbon that Mg mixes
The product 5 of preparation among the embodiment 5 and water soluble starch by 20: 0.25 mechanical mix grindings (add a spot of water during ball milling, rotating speed is 150 rev/mins, 2 hours) of weight ratio, are anhydrated the mixture drying that mixes; With the pyrolysis under high-purity argon gas of this mixture, the step of pyrolysis is: earlier be warmed up to 300 ℃ with 2 hours from room temperature, be warmed up to 500 ℃ with 10 hours from 300 ℃ again, then at 500 ℃ of constant temperature after 8 hours, drop to room temperature with 2 hours at last, obtained coating the inside composite particles of pyrolytic carbon layer; This composite particles is mixed (the 20g composite particles is mixed in the 80ml ethanol) wet-milling 2 hours (rotating speed is 300 rev/mins) with ethanol; take out the back drying and remove ethanol; obtain the secondary lithium battery cathode active material 6 that is used for of the present invention; this negative active core-shell material has nucleocapsid structure; outside average diameter is 20 microns; the transition metal oxide composite particles of the chromium oxide composition of active material Mg doping is contained in its inside; its outside has coated the carbon granule layer from the starch pyrolysis, and the weight ratio of its each several part is listed in table 2.
Embodiment 7, use liquid phase method legal system are equipped with the negative active core-shell material 7 of the chromium oxide of Ni doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 7 of the chromium oxide of Ni doping with nickel chloride, calcine 12 hours down at 600 ℃ after the presoma pre-burning after oven dry, all the other parameters are with embodiment 1, obtain a series of end products that are used for secondary lithium battery cathode active material 7 of the present invention, average grain diameter is 500 nanometers.
Embodiment 8, use pyrolysismethod to prepare the composite material of core-shell structure 8 of the formation of chromium oxide/carbon that Ni mixes
(draw ratio is 100: 1 with multi-walled carbon nano-tubes as conductive additive with the product 7 of preparation among the embodiment 7, length is 20 microns, diameter 50 nanometers) mix by 20: 1 weight ratios, (rotating speed is 500 rev/mins to mechanical ball milling, 6 hours), obtain inner composite particles; (2) should the inside composite particles and glucose by the wet-milling (add a spot of distilled water, rotating speed is 150 rev/mins, 1 hour) of 1: 1 weight ratio machinery, obtain finely dispersed mixture; (3) with this mixture, (volume ratio is 1: 4 under the mist that contains ethene and high pure nitrogen, flow is 200ml/ minute, the tube furnace volume is 0.02 cubic metre), 700 ℃ of pyrolysis in tube furnace (were raised to 700 ℃ with 7 hours from room temperature earlier, 700 ℃ of constant temperature 72 hours, again with dropping to room temperature in 2 hours), obtain the secondary lithium battery cathode active material 8 that is used for of the present invention, this negative active core-shell material has nucleocapsid structure, and Ni doping Cr is contained in its inside 2O 3Transition metal oxide composite particles with the multi-walled carbon nano-tubes composition, its outside has coated the carbon granule layer from the glucose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from ethylene pyrolysis, and outside average diameter is 15 microns, and the weight ratio of its each several part is listed in table 2.
Embodiment 9, use liquid phase method legal system are equipped with the negative active core-shell material 9 of the chromium oxide of Cu doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 9 of the chromium oxide of Cu doping with copper chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 9 of the present invention with embodiment 7, and average grain diameter is 600 nanometers.
Embodiment 10, use pyrolysismethod to prepare the composite material of core-shell structure 10 of the formation of chromium oxide/carbon that Cu mixes
The product 9 of preparation among the embodiment 9 is mixed with the weight ratio of pressing 20: 1 as the carbon fiber (diameter is 200 nanometers, and length is 10 microns) of conductive additive, and mechanical ball milling (rotating speed is 500 rev/mins, 6 hours) obtains inner composite particles; (2) should the inside composite particles and cyclodextrin by 1: 1 weight ratio machinery mix grinding (rotating speed is 150 rev/mins, 1 hour), obtain finely dispersed mixture; (3) with the pyrolysis under high pure nitrogen of this mixture, the step of pyrolysis is: be warmed up to 400 ℃ with 4 hours from room temperature earlier, be warmed up to 1200 ℃ with 10 hours from 400 ℃ again, then at 1200 ℃ of constant temperature after 12 hours, drop to room temperature with 2 hours at last, obtained coating the inside composite particles of pyrolytic carbon layer; This composite particles is mixed (the 20g composite particles is mixed in the 80ml ethanol) wet-milling 2 hours (rotating speed is 300 rev/mins) with ethanol, take out the back drying and remove ethanol, get 600 orders after the screening to the powder between 300 orders; (4) (volume ratio is 1: 2 under the mist that contains acetylene and high pure nitrogen, flow is 100ml/ minute, the tube furnace volume is 0.02 cubic metre), 1200 ℃ of pyrolysis (were raised to 1200 ℃ with 2 hours from room temperature earlier in tube furnace, 1200 ℃ of constant temperature 1 hour, again with dropping to room temperature in 2 hours), obtain the secondary lithium battery cathode active material 10 that is used for of the present invention, this negative active core-shell material has nucleocapsid structure, the chromium oxide of active material Cu doping and the transition metal oxide composite particles that conductive black is formed are contained in its inside, its outside has coated the carbon granule layer from the cyclodextrin pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the acetylene pyrolysis, outside average diameter is 10 microns, and the weight ratio of its each several part is listed in table 2.
Embodiment 11, use liquid phase method prepare the negative active core-shell material 11 of the chromium oxide of Sn (+2) doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 11 of the chromium oxide of Sn (+2) doping with stannous chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 11 of the present invention with embodiment 7, and average grain diameter is 450 nanometers.
Embodiment 12, use pyrolysismethod to prepare the composite material of core-shell structure 12 of the formation of chromium oxide/carbon that Sn mixes
The preparation method who uses the pyrolysismethod preparation to be used for secondary lithium battery cathode active material 12 is similar to the preparation method of embodiment 2, just the raw material of step (2) RESEARCH OF PYROCARBON is industrial yellow starch gum, obtain the secondary lithium battery cathode active material 12 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the chromium oxide of active material Sn (+2) doping and the transition metal oxide composite particles that conductive black is formed are contained in its inside, its outside has coated the carbon granule layer from the yellow starch gum pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, outside average diameter is 5 microns, and the weight ratio of its each several part is listed in table 2.
Embodiment 13, use liquid phase method legal system are equipped with the negative active core-shell material 13 of the chromium oxide of Co doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 13 of the chromium oxide of Co doping with cobalt chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 13 of the present invention with embodiment 7, and average grain diameter is 500 nanometers.
Embodiment 14, use pyrolysismethod to prepare the composite material of core-shell structure 14 of the formation of chromium oxide/carbon that Co mixes
The preparation method who is used for secondary lithium battery cathode active material 14 is similar to the preparation method of embodiment 2, just step (1) conductive additive is that (length is 100 nanometers to Single Walled Carbon Nanotube, diameter is 5 nanometers), obtain the secondary lithium battery cathode active material 14 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the chromium oxide of active material Co doping and the transition metal oxide composite particles that Single Walled Carbon Nanotube is formed are contained in its inside, its outside has coated the carbon granule layer from the sucrose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, and the weight ratio of its each several part is listed in table 2.Outside average diameter is 10 microns.
Embodiment 15, use liquid phase method legal system are equipped with the negative active core-shell material 15 of the chromium oxide of Fe doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 15 of the chromium oxide of Fe doping with iron chloride, calcine 16 hours down at 600 ℃ after the presoma pre-burning after oven dry, all the other parameters are with embodiment 1, obtain a series of end products that are used for secondary lithium battery cathode active material 15 of the present invention, average grain diameter is 1 micron.
Embodiment 16, use pyrolysismethod to prepare the composite material of core-shell structure 16 of the formation of chromium oxide/carbon that Fe mixes
The preparation method of negative active core-shell material 16 is similar to the preparation method among the embodiment 2, just step (1) conductive additive is metal Cu powder (average grain diameter is 500 nanometers), obtain the secondary lithium battery cathode active material 16 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the chromium oxide of active material Fe doping and the transition metal oxide composite particles that carbon nano-fiber is formed are contained in its inside, its outside has coated the carbon granule layer from the sucrose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, and the weight ratio of its each several part is listed in table 2.Outside average diameter is 10 microns.
Embodiment 17, use liquid phase method legal system are equipped with the negative active core-shell material 17 of the chromium oxide of Ca doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 17 of the chromium oxide of Ca doping with calcium chloride, calcine 12 hours down at 500 ℃ after the presoma pre-burning after oven dry, all the other parameters are with embodiment 1, obtain a series of end products that are used for secondary lithium battery cathode active material 17 of the present invention, average grain diameter is 200 nanometers.
Embodiment 18, use pyrolysismethod to prepare the composite material of core-shell structure 18 of the formation of chromium oxide/carbon that Ca mixes
The product 17 of preparation among the embodiment 17 is mixed by 4: 1 weight ratio with Ag powder (diameter is 100 nanometers) as conductive additive, (rotating speed is 500 rev/mins behind the mechanical ball milling, 6 hours), with the heat treatment under high pure nitrogen of this mixture, heat treated step is: be warmed up to 600 ℃ with 2 hours from room temperature earlier, after 1 hour, drop to room temperature with 2 hours at 600 ℃ of constant temperature again, obtain the inside composite particles of surface coverage carbon-coating; (2) should put into an autoclave by the inside composite particles, in autoclave, add 50% amidin in advance, compactedness is 95%, the weight ratio of starch and inner composite particles is 1: 2, reactor was heated 72 hours at 250 ℃, the black composite particles that produces is filtered, obtain coating the inside composite particles of carbon-coating; (3) will coat the inside composite particles of carbon-coating, pyrolysis under high pure nitrogen, the step of pyrolysis is: be warmed up to 300 ℃ with 4 hours from room temperature earlier, be warmed up to 750 ℃ with 5 hours from 300 ℃ again, then at 750 ℃ of constant temperature after 12 hours, drop to room temperature with 2 hours at last, obtained coating the inside composite particles of pyrolytic carbon layer; (4) (volume ratio is 1: 1 under the mist that contains benzene and high pure nitrogen, flow is 100ml/ minute, the tube furnace volume is 0.02 cubic metre), 700 ℃ of CVD pyrolysis (were raised to 700 ℃ with 3 hours from room temperature earlier in tube furnace, 700 ℃ of constant temperature 5 hours, again with dropping to room temperature in 2 hours), obtain the secondary lithium battery cathode active material 17 that is used for of the present invention, this negative active core-shell material has nucleocapsid structure, chromium oxide and the Ag powder that active material Ca mixes contained in its inside, and the outside has coated the carbon granule layer from the starch pyrolysis, and outermost layer has coated and utilized the carbon-coating of CVD from the benzene pyrolysis, outside average diameter is 400 nanometers, and the weight ratio of its each several part is listed in table 2.
Embodiment 19, use liquid phase method legal system are equipped with the negative active core-shell material 19 of the chromium oxide of Sr doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 19 of the chromium oxide of Sr doping with strontium chloride, calcine 12 hours down at 650 ℃ after the presoma pre-burning after oven dry, all the other parameters are with embodiment 1, obtain a series of end products that are used for secondary lithium battery cathode active material 19 of the present invention, average grain diameter is 1 micron.
Embodiment 20, use pyrolysismethod to prepare the composite material of core-shell structure 20 of the formation of chromium oxide/carbon that Sr mixes
The product 19 of preparation among the embodiment 19 is mixed by 2: 1 weight ratio with the acetylene black (average grain diameter is 10 nanometers) as conductive additive, and (rotating speed is 500 rev/mins, 6 hours) obtains inner composite particles behind the mechanical ball milling; (2) should put into an autoclave by the inside composite particles, in autoclave, add 40% the yellow starch gum aqueous solution in advance, compactedness is 20%, the weight ratio of yellow starch gum and inner composite particles is 10: 1, reactor was heated 24 hours at 190 ℃, after the black composite particles filtration that produces, obtain coating the inside composite particles of carbon-coating; (3) will coat the inside composite particles of carbon-coating, pyrolysis under high pure nitrogen, the step of pyrolysis is: be warmed up to 300 ℃ with 4 hours from room temperature earlier, be warmed up to 600 ℃ with 5 hours from 300 ℃ again, then at 600 ℃ of constant temperature after 5 hours, at last with dropping to room temperature in 2 hours, obtain the secondary lithium battery cathode active material 20 that is used for of the present invention, this negative active core-shell material has nucleocapsid structure, chromium oxide and the acetylene black that active material Sr mixes is contained in its inside, the outside has coated the carbon granule layer from the yellow starch gum pyrolysis, and outside average diameter is 500 nanometers, and the weight ratio of its each several part is listed in table 2.
Embodiment 21, use liquid phase method legal system are equipped with the negative active core-shell material 21 of the chromium oxide of Ti doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 21 of the chromium oxide of Ti doping with titanium chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 21 of the present invention with embodiment 7, and average grain diameter is 600 nanometers.
Embodiment 22, use pyrolysismethod to prepare the composite material of core-shell structure 22 of the formation of chromium oxide/carbon that Ti mixes
The preparation method of chromium oxide/carbon nucleocapsid composite construction negative active core-shell material 22 that Ti mixes is similar to the preparation method among the embodiment 2, just step (1) conductive additive is acetylene black (average grain diameter is 50 nanometers), obtain the secondary lithium battery cathode active material 22 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the chromium oxide of active material Ti doping and the transition metal oxide composite particles that acetylene black is formed are contained in its inside, its outside has coated the carbon granule layer from the sucrose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, outside average diameter is 1 micron, and the weight ratio of its each several part is listed in table 2.
Embodiment 23, use liquid phase method prepare the negative active core-shell material 23 of the chromium oxide of Mn (+4) doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 23 of the chromium oxide of Mn (+4) doping with manganese chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 23 of the present invention with embodiment 7, and average grain diameter is 550 nanometers.
Embodiment 24, use pyrolysismethod to prepare the composite material of core-shell structure 24 of the formation of chromium oxide/carbon that Mn mixes
The preparation method who contains chromium oxide/carbon nucleocapsid composite construction negative active core-shell material 24 that Mn (+4) mixes is similar to the preparation method among the embodiment 6, just step (1) conductive additive is that (length is 10 microns to the Cu nanofiber, diameter is 200 nanometers), obtain the secondary lithium battery cathode active material 24 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the chromium oxide of active material Mn (+4) doping and the transition metal oxide composite particles that acetylene black is formed are contained in its inside, its outside has coated the carbon granule layer from the glucose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from ethylene pyrolysis, outside average diameter is 10 microns, and the weight ratio of its each several part is listed in table 2.
Embodiment 25, use liquid phase method legal system are equipped with the negative active core-shell material 25 of the chromium oxide of Zn doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 25 of the chromium oxide of Zn doping with zinc chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 25 of the present invention with embodiment 7, and average grain diameter is 650 nanometers.
Embodiment 26, use pyrolysismethod to prepare the composite material of core-shell structure 26 of the formation of chromium oxide/carbon that Zn mixes
The preparation method who contains chromium oxide/carbon nucleocapsid composite construction negative active core-shell material 26 that Zn mixes is similar to the preparation method among the embodiment 2, obtain the secondary lithium battery cathode active material 26 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the composite particles of active material silicon and conductive black composition is contained in its inside, its outside has coated the carbon granule layer from the sucrose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, 10 microns of average grain diameters.The weight ratio of its each several part is listed in table 2.
Embodiment 27, use liquid phase method legal system are equipped with the negative active core-shell material 27 of the chromium oxide of Ce (+4) doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 27 of the chromium oxide of Ce (+4) doping with cerium chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 27 of the present invention with embodiment 7, and average grain diameter is 650 nanometers.
Embodiment 28, use pyrolysismethod to prepare the composite material of core-shell structure 28 of the formation of chromium oxide/carbon that Ce mixes
The preparation method of chromium oxide/carbon nucleocapsid composite construction negative active core-shell material 28 that Ce (+4) mixes is similar to the preparation method among the embodiment 2, be after chromium oxide that step (1) is mixed Ce (+4) and superfine graphite powder (average grain diameter is 1 micron) are mixed together ball milling, again with the sucrose mixed pyrolysis, obtain the secondary lithium battery cathode active material 28 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the chromium oxide that active material Ce (+4) mixes is contained in its inside, and the transition metal oxide composite particles of conductive black composition, its outside has coated the carbon granule layer from the sucrose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, 15 microns of average grain diameters.The weight ratio of its each several part is listed in table 2.
Embodiment 29, use liquid phase method legal system are equipped with the negative active core-shell material 29 of the chromium oxide of Sn (+4) doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 29 of the chromium oxide of Sn (+4) doping with stannic chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 29 of the present invention with embodiment 7, and average grain diameter is 550 nanometers.
Embodiment 30, the preparation of use pyrolysismethod contain the negative active core-shell material 30 of the chromium oxide/carbon nucleocapsid structure of Sn (+4) doping
The preparation method of chromium oxide/carbon nucleocapsid composite construction negative active core-shell material 30 that Sn (+4) mixes is similar to the preparation method among the embodiment 2, obtain the secondary lithium battery cathode active material 30 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the chromium oxide of active material Sn (+4) doping and the composite particles that conductive black is formed are contained in its inside, its outside has coated the carbon granule layer from the sucrose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, 10 microns of average grain diameters.The weight ratio of its each several part is listed in table 2.
Embodiment 31, use liquid phase method legal system are equipped with the negative active core-shell material 31 of the chromium oxide of Mo doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 31 of the chromium oxide of Mo doping with molybdenum chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 31 of the present invention with embodiment 7, and average grain diameter is 500 nanometers.
Embodiment 32, the preparation of use pyrolysismethod contain the negative active core-shell material 32 of the chromium oxide/carbon nucleocapsid structure of Mo doping
The preparation method of chromium oxide/carbon nucleocapsid composite construction negative active core-shell material 32 that Mo mixes is similar to the preparation method among the embodiment 2, just step (1) conductive additive is the superfine graphite powder, obtain the secondary lithium battery cathode active material 32 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the chromium oxide of active material Mo doping and the transition metal oxide composite particles that the superfine graphite powder is formed are contained in its inside, its outside has coated the carbon granule layer from the sucrose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, 15 microns of average grain diameters.The weight ratio of its each several part is listed in table 2.
Embodiment 33, use liquid phase method prepare the negative active core-shell material 33 of the chromium oxide of Zr doping
Press the stoichiometric proportion shown in the table 1, with a certain amount of CrCl 3Use liquid phase method to prepare the negative active core-shell material 33 of the chromium oxide of Zr doping with zirconium chloride, method obtains a series of end products that are used for secondary lithium battery cathode active material 33 of the present invention with embodiment 7, and average grain diameter is 600 nanometers.
Embodiment 34, use pyrolysismethod prepare the negative active core-shell material 34 of the chromium oxide/carbon nucleocapsid structure of Zr doping
The preparation method of chromium oxide/carbon nucleocapsid composite construction negative active core-shell material 34 that Zr mixes is similar to the preparation method among the embodiment 6, just step (1) conductive additive is a conductive carbon black, obtain the secondary lithium battery cathode active material 34 that is used for of the present invention at last, this negative active core-shell material has nucleocapsid structure, the negative active core-shell material of the chromium oxide that active material Zr mixes and the transition metal oxide composite particles that conductive carbon black is formed are contained in its inside, its outside has coated the carbon granule layer from the sucrose pyrolysis, outermost layer has coated and has utilized the carbon-coating of CVD from the toluene pyrolysis, 20 microns of average grain diameters.The weight ratio of its each several part is listed in table 2.
Embodiment 35, preparation mix negative active core-shell material 35
The negative active core-shell material of the chromium oxide that the Li of embodiment 1 preparation is mixed and modified natural graphite negative material mix (rotating speed is 150 rev/mins, 1 hour) in 20: 80 ratio mechanical ball milling, obtain mixing negative material 35.
The preparation of the negative pole of Experimental cell, anodal preparation, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1.Charging and discharging curve and cyclicity are seen Fig. 5, Fig. 6.
Embodiment 36, preparation mix negative active core-shell material 36
The negative active core-shell material of the chromium oxide that the Li of embodiment 1 preparation is mixed and MCMB negative material obtain mixing negative material 36 in 50: 50 ratio mechanical mixture (rotating speed is 150 rev/mins, 1 hour).
The preparation of the negative pole of Experimental cell, anodal preparation, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1.The chemical property of embodiment 36 and embodiment 35 are similar.
Embodiment 37, preparation mix negative active core-shell material 37
The negative active core-shell material of the chromium oxide that the Li that embodiment 1 is prepared mixes and the ratio mechanical mixture (rotating speed be 150 rev/min, 1 hour) of hard charcoal ball negative material in 5: 95 obtain mixing negative material 37.
The preparation of the negative pole of Experimental cell, anodal preparation, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1.Charging and discharging curve and cyclicity are seen Fig. 7, Fig. 8.
The preparation of the negative pole of embodiment 3,5,7,9,11,13,15,17,19,21,23,25,27,29,31 and 33 Experimental cell, anodal preparation, Experimental cell assembling and method of testing are with embodiment 1, and the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 1.
The composition of table 1, hetero-atom doping chrome green negative active core-shell material and simulated battery thereof discharge and recharge data
Embodiment Hetero-atom doping M Chemical property
Kind Cr 2-xM xO 3Middle X value Reversible capacity (MAH/gram) Coulombic efficiency
1 Li 0.002 850 69
1 Li 0.08 730 61
1 Li 0.12 620 58
1 Li 0.16 540 43
1 Li 0.2 480 41
1 Li 1 180 36
3 Ag 0.002 830 67
3 Ag 0.16 520 43
3 Ag 1 380 46
5 Mg 0.002 820 68
5 Mg 0.16 320 42
5 Mg 1 380 46
7 Ni 0.002 860 67
7 Ni 0.16 520 43
7 Ni 1 680 64
9 Cu 0.002 760 63
9 Cu 0.16 520 43
9 Cu 1 580 62
11 Sn 0.002 860 67
11 Sn 0.16 520 43
13 Co 0.002 760 69
13 Co 0.16 520 43
13 Co 1 780 68
15 Fe 0.002 780 68
15 Fe 0.16 580 43
15 Fe 1 670 66
17 Ca 0.002 710 67
17 Ca 0.16 510 43
17 Ca 1 380 38
19 Sr 0.002 730 67
19 Sr 0.16 540 43
19 Sr 1 410 40
21 Ti 0.002 810 69
21 Ti 0.16 530 43
21 Ti 1 360 40
23 Mn 0.002 860 69
23 Mn 0.16 520 43
23 Mn 1 680 65
25 Zn 0.002 660 67
25 Zn 0.16 420 43
25 Zn 1 360 34
27 Ce 0.002 740 66
27 Ce 0.16 510 48
27 Ce 1 410 42
29 Sn 0.002 810 69
29 Sn 0.16 620 58
29 Sn 1 680 64
31 Mo 0.002 660 63
31 Mo 0.16 420 51
31 Mo 1 280 44
33 Zr 0.002 750 70
The preparation of the negative pole of embodiment 2,4,6,8,10,12,14,16,18,20,22,24,26,28,30,32 and 34 Experimental cell, anodal preparation, Experimental cell assembling and method of testing are with embodiment 1, the assembling of simulated battery and test are with embodiment 1, and its test result is listed in table 2.
The composition of table 2, hetero-atom doping chrome green/carbon nucleocapsid structure negative active core-shell material and simulated battery thereof discharge and recharge data
Embodiment Negative active core-shell material is formed (total weight percent) Chemical property
Kernel portion Outer shell
Active material Conductive additive Reversible capacity (MAH/gram) Coulombic efficiency
Doped chemical Molecular formula Percentage Pyrolytic carbon layer+CVD carbon-coating
2 Li Li 0.001Cr 1.999O 3 85 8.5 6.5 780 76
2 Li Li 0.08Cr 1.97O 3 85 8.5 6.5 650 74
2 Li Li 0.12Cr 1.96O 3 85 8.5 6.5 610 73
2 Li Li 0.16Cr 1.95O 3 85 8.5 6.5 510 72
2 Li Li 0.4Cr 1.8O 3 85 8.5 6.5 480 71
2 Li Li 1.5Cr 1.5O 3 85 8.5 6.5 260 64
4 Ag Ag 0.04Cr 1.98O 3 85 8.5 6.5 480 78
6 Mg Mg 0.02Cr 1.99O 3 90 0 10 850 77
8 Ni Ni 0.02Cr 1.99O 3 90 4.5 5.5 850 77
10 Cu Cu 0.02Cr 1.99O 3 90 4.5 5.5 830 85
12 Sn Sn 0.02Cr 1.99O 3 85 8.5 6.5 770 78
14 Co Co 0.02Cr 1.99O 3 85 8.5 6.5 700 77
16 Fe Fe 0.02Cr 1.99O 3 85 8.5 6.5 700 79
18 Ca Ca 0.02Cr 1.99O 3 40 10 50 410 78
20 Sr Sr 0.02Cr 1.99O 3 40 20 40 420 78
22 Ti Ti 0.02Cr 1.97O 3 85 8.5 6.5 750 85
24 Mn Mn 0.02Cr 1.97O 3 90 4.5 5.5 780 78
26 Zn Zn 0.02Cr 1.97O 3 85 8.5 6.5 720 74
28 Ce Ce 0.02Cr 1.97O 3 85 8.5 6.5 350 84
30 Sn Sn 0.02Cr 1.97O 3 85 8.5 6.5 500 80
32 Mo Mo 0.02Cr 1.97O 3 85 8.5 6.5 700 78
34 Zr Zr 0.02Cr 1.97O 3 90 4.5 5.5 770 76

Claims (10)

1, a kind of chromium-base negative electrode active material that is used for serondary lithium battery, it is the oxide of heteroatomic transition metal chromium of having mixed, its chemical formula is Cr 2-xM xO 3, 0.001≤x≤1.5 wherein; Hetero-atom M is Li, Ag, Mg, Ni, Cu, Zn, Sn, Co, Fe, Ca, Sr, Ti, Mn, Ce, Sn, Mo or Zr; The particle diameter of material granule is 50 nanometers to 20 micron.
2, the chromium-base negative electrode active material that is used for serondary lithium battery as claimed in claim 1 is characterized in that, also comprises conductive additive, and wherein conductive additive accounts for 1～20wt% of the total weight of material.
3, the chromium-base negative electrode active material that is used for serondary lithium battery as claimed in claim 2 is characterized in that, described conductive additive is graphite powder, conductive black, acetylene black, metal powder, carbon nano-tube, carbon fiber or metallic fiber.
4, the chromium-base negative electrode active material that is used for serondary lithium battery as claimed in claim 3 is characterized in that, the particle diameter of described graphite powder, conductive black, acetylene black or metal powder is 10 nanometers to 10 micron.
5, the chromium-base negative electrode active material that is used for serondary lithium battery as claimed in claim 3 is characterized in that, the diameter of described carbon nano-tube, carbon fiber or metallic fiber is 5～200nm, and length is 10 nanometers to 10 micron.
6, as the described chromium-base negative electrode active material that is used for serondary lithium battery of one of claim 1～5, it is characterized in that, also be included in outside " nuclear " by the mixture of the oxide of the oxide of described transition metal chromium or transition metal chromium and conductive additive, one or more layers the carbon film or " shell " of carbon granule are arranged, its center partly account for material total weight 50～99%, shell partly account for material total weight 1～50%.
7, the described chromium-base negative electrode active material that is used for serondary lithium battery of one of a kind of claim 1～5 purposes of making the negative pole of serondary lithium battery.
8, the described chromium-base negative electrode active material that is used for serondary lithium battery of a kind of claim 6 purposes of making the negative pole of serondary lithium battery.
9, the described chromium-base negative electrode active material that is used for serondary lithium battery of one of a kind of claim 1～5 mixes the purposes that is used for the secondary lithium battery cathode material with other existing negative material, and the described chromium-base negative electrode active material that is used for serondary lithium battery accounts for 20～98wt% of total negative material weight.
10, the described chromium-base negative electrode active material that is used for serondary lithium battery of a kind of claim 6 mixes the purposes that is used for the secondary lithium battery cathode material with other existing negative material, and the described chromium-base negative electrode active material that is used for serondary lithium battery accounts for 20～98wt% of total negative material weight.
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CN102185142A (en) * 2011-04-08 2011-09-14 厦门大学 Composite carbon cathode material for lithium ion battery and preparation method thereof
CN101958411B (en) * 2009-07-13 2012-09-05 北京工业大学 CoO-Co composite material with core-shell structure and preparation method thereof
CN102694154A (en) * 2012-05-30 2012-09-26 中国科学技术大学 Modified lithium ion battery cathode material and preparation method thereof
CN103311534A (en) * 2013-06-08 2013-09-18 苏州诺信创新能源有限公司 Preparation method of composite negative material of lithium-ion battery
CN107482199A (en) * 2017-08-08 2017-12-15 南陵县生产力促进中心 It is a kind of for the chromium oxide of cathode of lithium battery and the preparation method of carbon nano tube compound material
CN109075383A (en) * 2016-06-08 2018-12-21 株式会社钟化 Lithium ion secondary battery and battery pack
CN113839104A (en) * 2020-06-24 2021-12-24 比亚迪股份有限公司 Lithium battery cathode and lithium battery

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JPS59132569A (en) * 1983-01-19 1984-07-30 Matsushita Electric Ind Co Ltd Battery
DE69827700T2 (en) * 1997-05-22 2005-10-06 Matsushita Electric Industrial Co., Ltd., Kadoma Secondary battery with non-aqueous electrolyte
JP3670878B2 (en) * 1999-03-25 2005-07-13 三洋電機株式会社 Lithium secondary battery
JP3617447B2 (en) * 1999-12-01 2005-02-02 松下電器産業株式会社 Lithium secondary battery

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CN101958411B (en) * 2009-07-13 2012-09-05 北京工业大学 CoO-Co composite material with core-shell structure 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
CN102694154A (en) * 2012-05-30 2012-09-26 中国科学技术大学 Modified lithium ion battery cathode material and preparation method thereof
CN103311534A (en) * 2013-06-08 2013-09-18 苏州诺信创新能源有限公司 Preparation method of composite negative material of lithium-ion battery
CN109075383A (en) * 2016-06-08 2018-12-21 株式会社钟化 Lithium ion secondary battery and battery pack
CN107482199A (en) * 2017-08-08 2017-12-15 南陵县生产力促进中心 It is a kind of for the chromium oxide of cathode of lithium battery and the preparation method of carbon nano tube compound material
CN113839104A (en) * 2020-06-24 2021-12-24 比亚迪股份有限公司 Lithium battery cathode and lithium battery
CN113839104B (en) * 2020-06-24 2023-12-12 比亚迪股份有限公司 Lithium battery cathode and lithium battery

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