CN104009217A - Preparing method for submicron particles of nickel-manganese-base lithium ion battery anode material - Google Patents

Preparing method for submicron particles of nickel-manganese-base lithium ion battery anode material Download PDF

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CN104009217A
CN104009217A CN201410261155.0A CN201410261155A CN104009217A CN 104009217 A CN104009217 A CN 104009217A CN 201410261155 A CN201410261155 A CN 201410261155A CN 104009217 A CN104009217 A CN 104009217A
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lithium ion
nitrate
submicron particles
nickel
base lithium
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熊岳平
梁成豪
刘连宝
杨路
霍华
戴长松
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

Abstract

The invention relates to a preparing method of a nickel-manganese-base lithium ion battery anode material, in particular to a preparing method for submicron particles for the nickel-manganese-base lithium ion battery anode material. The technical problems that a material obtained through an existing preparing method for the nickel-manganese-base lithium ion battery anode material is large in particle size and poor in electrical property are solved. The preparing method includes the steps that according to the chemical formula Li (MxNiyMn1-x-y) O2, a electrostatic spinning precursor solution is prepared through metal nitrates, N, N-dimethyl formamide and polyvinylpyrrolidone; the electrostatic spinning precursor solution is spun into nano-fibers through an electrostatic spinning machine, and the nano-fibers are calcinated to obtain the submicron particles for the nickel-manganese-base lithium ion battery anode material. The particle diameter of the submicron particles is 50 nm-200 nm, the specific discharge capacity under the condition of 1000 mA/g large current reaches 110 mAh/g, and only differs from that under the condition of 20 mA/g current by 39.3 mAh/g. The submicron particles for the nickel-manganese-base lithium ion battery anode material can be used in a high-power lithium ion battery.

Description

A kind of preparation method of nickel manganese base lithium ion cell positive material submicron particles
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries.
Background technology
Along with constantly giving prominence to of energy environment issues, brought up the fast development of new forms of energy.Lithium ion battery is compared with secondary cells such as traditional lead acid accumulator, ickel-cadmium cell, Ni-MH batteries, have that operating voltage is high, the advantage such as energy density is large, have extended cycle life, self-discharge rate is little, low pollution, memory-less effect, thereby obtained paying close attention to widely and development faster.In lithium ion battery, electrode material is the core in battery, and with respect to negative material, the research of anode material for lithium-ion batteries relatively lags behind, and becomes a key factor of restriction lithium ion battery development.
Traditional cobalt acid lithium is to realize the earliest business-like anode material for lithium-ion batteries, but the limited cost of cobalt resource is higher and environment is had to pollution, and fail safe is poor, has limited the development of cobalt acid lithium material in large-sized battery.Lithium nickelate, with respect to the sour lithium material of cobalt, has identical space structure, and Ni element to compare Co element comparatively friendly to environment, be considered to more promising anode material for lithium-ion batteries, but its synthetic difficulty, thermal stability is poor has restricted its development.LiMn2O4 is to environment nontoxic pollution-free, and manganese resource reserve is abundant, as lithium ion anode material, has also obtained research widely, but synthetic pure phase material difficulty, the not high shortcoming that becomes this material of specific discharge capacity.Lithium ion battery ternary or polynary positive pole material, just because of cooperative effect, have the common feature of cobalt acid lithium, lithium nickelate and manganese and oxygen compound.The Chinese patent that is 201310427972.4 as application number discloses the Polymer-pyrolysis preparation method of lithium-rich manganese-based anode material for a kind of lithium ion battery, the method is added drop-wise to lithium, nickel, cobalt, manganese metal salt solution in acrylic acid solution, to add thermal agitation, add a small amount of ammonium persulfate, polymerization forms jelly, after jelly is dry, grinding, pre-burning and sintering obtain lithium-rich anode material.Application number is the preparation method that the Chinese patent of 201310614691.X discloses the rich lithium composite positive pole of a kind of multiplying power, the method is by the precipitation of metal ion, then heat-treat, obtain oxide precursor, oxide precursor is mixed with lithium-containing compound, hydrothermal treatment consists, obtains pre-reaction presoma again, heat treatment again, obtains rich lithium composite positive pole.No matter that Polymer-pyrolysis method or precipitation are in conjunction with heat treating process, the particle of preparation is all at micron order, and lattice is grown imperfection, and this will cause cycle performance not good enough, larger particle of while polarizes larger in high current charge-discharge situation, is unfavorable for working under large current condition.Therefore prepare lattice structure and grow that to improve stable small-particulate materials necessary.
Summary of the invention
The present invention is that will to solve the particle that the preparation method of existing anode material for lithium-ion batteries obtains large, the technical problem of poor electrical performance, and a kind of preparation method of nickel manganese base lithium ion cell positive material submicron particles is provided.
The preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles of the present invention carries out according to the following steps:
One, according to stoichiometric equation Li (M xni ymn 1-x-y) mol ratio of Ni, Mn and M takes in O2 nickel nitrate, manganese nitrate, the nitrate of M and excessive lithium nitrate, first the nitrate of nickel nitrate, manganese nitrate and M is added to N, in dinethylformamide, after at room temperature magnetic agitation to all inorganic salts all dissolve, the lithium nitrate that adds polyvinylpyrrolidone and take, be stirred to polyvinylpyrrolidone and dissolve completely, obtain electrostatic spinning precursor liquid; Li (M wherein xni ymn 1-x-y) O 2middle M is the combination of one or more elements in Co, Fe and Al, 0 < x≤0.5,0 < y≤0.5, and x+y < 1;
Two, the spinning precursor liquid obtaining is injected to the syringe with stainless steel syringe needle of electrostatic spinning machine, between stainless steel syringe needle and stainless steel reception net, add direct voltage, constantly rotate stainless steel reception net and collect the nanofiber spraying from syringe needle;
Three, after spinning finishes, nanofiber on stainless steel collecting net is collected and puts into Muffle furnace, heating rate with 1 ℃/min～8 ℃/min under oxidizing atmosphere is warming up to constant temperature sintering 1～5h at 500 ℃ by room temperature, then the heating rate with 1 ℃/min～8 ℃/min is warming up to 700～900 ℃ of constant temperature sintering 2～20h, obtains nickel manganese base lithium ion cell positive material submicron particles.
Employing electrospinning process of the present invention obtains nanofiber, and nanofiber obtains nickel manganese base lithium ion cell positive material submicron particles through roasting again, and submicron particles particle size is at 50～200nm.The advantage that adopts method of electrostatic spinning to prepare nickel manganese base lithium ion cell positive material is to adopt the effect of high-voltage dc to make electrostatic spinning solution form superfine uniform nanofiber, greatly the restriction of degree material in three-dimensional diffusion and segregation, be conducive to improve the stable lattice degree of material, thereby improve the chemical property of material.Nanofiber is dispersed into less particle in the process of high temperature sintering uniformly, and the particle diameter of particle is controlled by the diameter of nanofiber, this makes comparatively homogeneous and be easy to control of granular size, submicron particles prepared by the present invention, particle diameter is little, can shorten the diffusion path of lithium ion, and then improve the specific discharge capacity of material under large current condition.Meanwhile, under the effect of high-voltage dc, interionic interaction is destroyed, makes in follow-up sintering process, and the lattice of nano particle is grown more perfect, has reduced cationic mixing degree in nano particle, can improve the chemical property of material.Nickel manganese base lithium ion cell positive material submicron particles specific discharge capacity under the large current condition of 1000mA/g prepared by the present invention reaches 110mAh/g, only differs 39mAh/g with specific discharge capacity under 20mA/g condition.Can be used in high-power lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the nickel manganese base lithium ion cell positive material Li (Fe of test 1 preparation 0.2ni 0.2mn 0.6) O 2the SEM photo of submicron particles;
Fig. 2 is the nickel manganese base lithium ion cell positive material Li (Fe of test 1 preparation 0.2ni 0.2mn 0.6) O 2the XRD spectra of submicron particles;
Fig. 3 is the nickel manganese base lithium ion cell positive material Li (Fe of test 1 preparation 0.2ni 0.2mn 0.6) O 2first circle charging and discharging curve figure;
Fig. 4 is the nickel manganese base lithium ion cell positive material Li (Co of test 2 preparations 0.2ni 0.5mn 0.3) O 2the SEM photo of submicron particles;
Fig. 5 is the nickel manganese base lithium ion cell positive material Li (Co of test 2 preparations 0.2ni 0.5mn 0.3) O 2the XRD spectra of submicron particles;
Fig. 6 is the nickel manganese base lithium ion cell positive material Li (Co of test 2 preparations 0.2ni 0.5mn 0.3) O 2the multiplying power of submicron particles battery and cycle performance figure.
Embodiment
Embodiment one: the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles of present embodiment carries out according to the following steps:
One, according to stoichiometric equation Li (M xni ymn 1-x-y) mol ratio of Ni, Mn and M takes in O2 nickel nitrate, manganese nitrate, the nitrate of M and excessive lithium nitrate, first the nitrate of nickel nitrate, manganese nitrate and M is added to N, in dinethylformamide, after at room temperature magnetic agitation to all inorganic salts all dissolve, the lithium nitrate that adds polyvinylpyrrolidone and take, be stirred to polyvinylpyrrolidone and dissolve completely, obtain electrostatic spinning precursor liquid; Li (M wherein xni ymn 1-x-y) O 2middle M is the combination of one or more elements in Co, Fe and Al, 0 < x≤0.5,0 < y≤0.5, and x+y < 1;
Two, the spinning precursor liquid obtaining is injected to the syringe with stainless steel syringe needle of electrostatic spinning machine, between stainless steel syringe needle and stainless steel reception net, add direct voltage, constantly rotate stainless steel reception net and collect the nanofiber spraying from syringe needle;
Three, after spinning finishes, nanofiber on stainless steel collecting net is collected and puts into Muffle furnace, heating rate with 1 ℃/min～8 ℃/min under oxidizing atmosphere is warming up to constant temperature sintering 1～5h at 500 ℃ by room temperature, then the heating rate with 1 ℃/min～8 ℃/min is warming up to 700～900 ℃ of constant temperature sintering 2～20h, obtains nickel manganese base lithium ion cell positive material submicron particles.
Embodiment two: present embodiment is different from embodiment one is that the addition of lithium nitrate in step 1 is stoichiometric proportion 1.02～1.15 times.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two be in step 1 in electrostatic spinning precursor liquid the total mass concentration of the nitrate of lithium nitrate, nickel nitrate, manganese nitrate and M be 8%～25%, the mass concentration of polyvinylpyrrolidone is 8～15%.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is that in step 1, M is that Fe element and Al element be take mol ratio as (1～3): 1 combination.Other are identical with one of embodiment one to three.
The mode that adopts Fe element to mix with Al element reduces the LiFeO that Fe element forms at a lower temperature 2dephasign.
Embodiment five: what present embodiment was different from one of embodiment one to four is that in step 2, stainless steel syringe needle internal diameter is 0.4～0.9mm.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five is that in step 2, stainless steel syringe needle and the direct voltage that receives between net are 15～30kV.Other is identical with one of embodiment one to six.
Embodiment seven: present embodiment is different from one of embodiment one to six be in step 2 syringe downward-sloping with angle horizontal plane be 10～25 °, make not occur on syringe needle drop.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different from one of embodiment one to seven is that the rotary speed that in step 2, stainless steel reception is netted is 10～50r/min.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is that the oxidizing atmosphere described in step 3 is air atmosphere or oxygen atmosphere.Other is identical with one of embodiment one to eight.
Adopt following verification experimental verification effect of the present invention:
Test one: the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles of this test carries out according to the following steps:
One, first take the conical flask that manganese nitrate aqueous solution that the mass concentration of 8.2333g is 50% is placed in 250mL, then add 3.2307g lithium nitrate, 3.1457g ferric nitrate, 2.2764g nickel nitrate, add again 120mLN, dinethylformamide, at room temperature use magnetic stirring apparatus to make after medicine dissolves completely, slowly add 15.00g polyvinylpyrrolidone, after polyvinylpyrrolidone dissolves completely, obtain the electrostatic spinning precursor liquid of thickness.In spinning solution, the total mass concentration of lithium nitrate, ferric nitrate, nickel nitrate, manganese nitrate is 11.6%, and the mass concentration of polyvinylpyrrolidone is 10.3%;
Two, the spinning precursor liquid obtaining is injected to the syringe of electrostatic spinning machine, this syringe is 0.5mm stainless steel syringe needle with internal diameter, syringe downward-sloping with angle horizontal plane be 15 °, make not occur on syringe needle drop, between stainless steel syringe needle and stainless steel reception net, add 25kV direct voltage, constantly rotate stainless steel and receive the nanofiber that net collection sprays from syringe needle; The rotary speed that stainless steel receives net is 30r/min;
Three, after spinning finishes, nanofiber on stainless steel collecting net is carefully collected and puts into Muffle furnace, heating rate with 5 ℃/min under oxidizing atmosphere is warming up to constant temperature sintering 5h at 500 ℃ by room temperature, and then with 5 ℃/min heating rate be warming up to 750 ℃ of constant temperature sintering 16h, obtain nickel manganese base lithium ion cell positive material submicron particles.
The composition of the nickel manganese base lithium ion cell positive material submicron particles of this test preparation is Li (Fe 0.2ni 0.2mn 0.6) O 2, as shown in Figure 1, as can be seen from Figure 1, the particle diameter of particle is 50～150nm to its SEM photo.
As shown in Figure 2, as can be seen from Figure 2, the half-peak breadth of diffraction maximum is wider, illustrates that grain diameter is less, its cell parameter: a for the XRD spectra of the nickel manganese base lithium ion cell positive material submicron particles of this test resulting materials: , c: , c/a:4.99, I 003/ I 104: 1.36, from the numerical value of c/a, be greater than 4.9 and I 003/ I 104value be greater than 1.2, good degree of crystallinity and lower cation mixing degree are described.
By the nickel manganese base lithium ion cell positive material submicron particles of this test preparation and conductive agent Super p Li and binding agent PVDF in mass ratio 80:10:10 with become electrode pastes, then be evenly coated in aluminum foil current collector, as positive pole, take lithium sheet as negative pole, the LiPF that the concentration of take is 1mol/L 6being dissolved in the ethylene carbonate that volume ratio is 1:1:1 (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mixed solution is electrolyte, be assembled into button cell, record the first circle charging and discharging curve of battery as shown in Figure 3, as can be seen from Figure 3, in the voltage range of 2.0V～4.7V, initial charge specific capacity reaches 210.4mAh/g, first discharge specific capacity is 173.9mAh/g, and first charge-discharge efficiency is 82.7%.
Test two: the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles of this test carries out according to the following steps:
One, first take the conical flask that manganese nitrate aqueous solution that the mass concentration of 3.3765g is 50% is placed in 250mL, then add 2.4099g lithium nitrate, 1.8497g cobalt nitrate, 4.6670g nickel nitrate, add again 100mLN, dinethylformamide, at room temperature use magnetic stirring apparatus that medicine is dissolved completely, then slowly add 11.00g polyvinylpyrrolidone, after polyvinylpyrrolidone dissolves completely, obtain the electrostatic spinning precursor liquid of thickness.In electrostatic spinning precursor liquid, lithium nitrate, cobalt nitrate, nickel nitrate, the total mass concentration of manganese nitrate are 12.3%, and the mass concentration of polyvinylpyrrolidone is 11.0%;
Two, the spinning precursor liquid obtaining is injected to the syringe of electrostatic spinning machine, this syringe is 0.5mm stainless steel syringe needle with internal diameter, syringe downward-sloping with angle horizontal plane be 15 °, make not occur on syringe needle drop, between stainless steel syringe needle and stainless steel reception net, add 25kV direct voltage, constantly rotate stainless steel and receive the nanofiber that net collection sprays from syringe needle; The rotary speed that stainless steel receives net is 30r/min;
Three, after spinning finishes, nanofiber on stainless steel collecting net is carefully collected and puts into Muffle furnace, heating rate with 5 ℃/min under oxidizing atmosphere is warming up to constant temperature sintering 2h at 500 ℃ by room temperature, and then with 5 ℃/min heating rate be warming up to 900 ℃ of constant temperature sintering 5h, obtain nickel manganese base lithium ion cell positive material submicron particles.
The composition of the nickel manganese base lithium ion cell positive material submicron particles of this test preparation is Li (Co 0.2ni 0.5mn 0.3) O 2, as shown in Figure 4, as can be seen from Figure 4, the particle diameter of particle is 50～200nm to its SEM photo.
The nickel manganese base lithium ion cell positive material Li (Co of this test resulting materials 0.2ni 0.5mn 0.3) O 2the XRD spectra of submicron particles as shown in Figure 5, its cell parameter: a: , c: , c/a:4.96, I 003/ I 104: 1.42, from the numerical value of c/a, be greater than 4.9 and I 003/ I 104value be greater than 1.2, good degree of crystallinity and lower cation mixing degree are described.It can also be seen that from Fig. 5, the Li (Co of this test preparation 0.2ni 0.5mn 0.3) O 2it is mutually all right that submicron particles becomes, and in figure, all can correspondingly go up the peak position peak position all with standard spectrogram, and without the appearance at dephasign peak, half-peak breadth is narrower, and the degree of crystallinity of particle is better.
By the nickel manganese base lithium ion cell positive material Li (Co of this test preparation 0.2ni 0.5mn 0.3) O 2submicron particles and conductive agent Super p Li and binding agent PVDF in mass ratio 80:10:10 with become lotion, be then evenly coated in aluminum foil current collector, as positive pole, the LiPF that the concentration of take is 1mol/L 6being dissolved in the ethylene carbonate that volume ratio is 1:1:1 (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mixed solution is electrolyte, as shown in Figure 6, the charging and discharging currents size adopting in figure is followed successively by cycle performance figure after multiplying power and multiplying power test from front to back: 20mA/g, 40mA/g, 100mA/g, 200mA/g, 1000mA/g, 200mA/g, 100mA/g, 40mA/g, 20mA/g, 100mA/g.As can be seen from Figure 6, when charging and discharging currents is 1000mA/g, specific capacity is 110.0mAh/g, and when charging and discharging currents is 20mA/g, specific capacity is 149.3mAh/g.Li (Co prepared by method of electrostatic spinning 0.2ni 0.5mn 0.3) O 2submicron material shows excellent high rate performance in the voltage range of 2.8V～4.3V, it is only 39.3mAh/g that specific discharge capacity when charging and discharging currents is 20mA/g and 1000mA/g differs, after multiplying power test, with 100mA/g, carry out loop test, after 150 circulations, capability retention is 94.0%.
Test three: the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles of this test carries out according to the following steps:
One, first take the conical flask that manganese nitrate aqueous solution that the mass concentration of 9.9721g is 50% is placed in 250mL, then add 3.9135g lithium nitrate, 2.8572g ferric nitrate, 0.8800g aluminum nitrate and 2.7562g nickel nitrate, add 150mLN, dinethylformamide, at room temperature use magnetic stirring apparatus that medicine is dissolved completely, then slowly add 17.50g polyvinylpyrrolidone, after polyvinylpyrrolidone dissolves completely, obtain the electrostatic spinning precursor liquid of thickness.In electrostatic spinning precursor liquid, lithium nitrate, ferric nitrate, aluminum nitrate, nickel nitrate, the total mass concentration of manganese nitrate are 11.3%, and the mass concentration of polyvinylpyrrolidone is 9.7%.；
Two, the spinning precursor liquid obtaining is injected to the syringe of electrostatic spinning machine, this syringe is 0.5mm stainless steel syringe needle with internal diameter, syringe downward-sloping with angle horizontal plane be 15 °, make not occur on syringe needle drop, between stainless steel syringe needle and stainless steel reception net, add 25kV direct voltage, constantly rotate stainless steel and receive the nanofiber that net collection sprays from syringe needle; The rotary speed that stainless steel receives net is 30r/min;
Three, after spinning finishes, nanofiber on stainless steel collecting net is carefully collected and puts into Muffle furnace, heating rate with 2 ℃/min under oxidizing atmosphere is warming up to constant temperature sintering 5h at 500 ℃ by room temperature, and then with 2 ℃/min heating rate be warming up to 750 ℃ of constant temperature sintering 16h, obtain nickel manganese base lithium ion cell positive material submicron particles.
The nickel manganese base lithium ion cell positive material of this test preparation is Li (Fe 0.15al 0.05ni 0.2mn 0.6) O 2.The degree of crystallinity of particle is better.To make Anode and battery with method identical in test 1, the specific discharge capacity of test battery when charging and discharging currents is 1000mA/g is 63.8mAh/g.

Claims (8)

1. a preparation method for nickel manganese base lithium ion cell positive material submicron particles, is characterized in that the method carries out according to the following steps:
One, according to stoichiometric equation Li (M xni ymn 1-x-y) mol ratio of Ni, Mn and M takes in O2 nickel nitrate, manganese nitrate, the nitrate of M and excessive lithium nitrate, first the nitrate of nickel nitrate, manganese nitrate and M is added to N, in dinethylformamide, after at room temperature magnetic agitation to all inorganic salts all dissolve, the lithium nitrate that adds polyvinylpyrrolidone and take, be stirred to polyvinylpyrrolidone and dissolve completely, obtain electrostatic spinning precursor liquid; Li (M wherein xni ymn 1-x-y) O 2middle M is the combination of one or more elements in Co, Fe and Al, 0 < x≤0.5,0 < y≤0.5, and x+y < 1;
Two, the spinning precursor liquid obtaining is injected to the syringe with stainless steel syringe needle of electrostatic spinning machine, between stainless steel syringe needle and stainless steel reception net, add direct voltage, constantly rotate stainless steel reception net and collect the nanofiber spraying from syringe needle;
Three, after spinning finishes, nanofiber on stainless steel collecting net is collected and puts into Muffle furnace, heating rate with 1 ℃/min～8 ℃/min under oxidizing atmosphere is warming up to constant temperature sintering 1～5h at 500 ℃ by room temperature, then the heating rate with 1 ℃/min～8 ℃/min is warming up to 700～900 ℃ of constant temperature sintering 2～20h, obtains nickel manganese base lithium ion cell positive material submicron particles.
2. the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles according to claim 1, the addition that it is characterized in that lithium nitrate in step 1 is stoichiometric proportion 1.02～1.15 times.
3. the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles according to claim 1 and 2, it is characterized in that in step 1 in electrostatic spinning precursor liquid that the total mass concentration of the nitrate of lithium nitrate, nickel nitrate, manganese nitrate and M is 8%～25%, the mass concentration of polyvinylpyrrolidone is 8%～15%.
4. the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles according to claim 1 and 2, is characterized in that in step 1, M is that Fe element and Al element be take mol ratio as (1～3): 1 combination.
5. the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles according to claim 1 and 2, is characterized in that in step 2, stainless steel syringe needle internal diameter is 0.4～0.9mm.
6. the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles according to claim 1 and 2, is characterized in that stainless steel syringe needle in step 2 and the direct voltage receiving between net are 15～30kV.
7. the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles according to claim 1 and 2, is characterized in that the rotary speed of stainless steel reception net in step 2 is 10～50r/min.
8. the preparation method of a kind of nickel manganese base lithium ion cell positive material submicron particles according to claim 1 and 2, is characterized in that the oxidizing atmosphere described in step 3 is air atmosphere or oxygen atmosphere.
CN201410261155.0A 2014-06-13 2014-06-13 Preparing method for submicron particles of nickel-manganese-base lithium ion battery anode material Pending CN104009217A (en)

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