CN104201370A - Positive electrode material of lithium ion battery, and preparation method thereof - Google Patents

Positive electrode material of lithium ion battery, and preparation method thereof Download PDF

Info

Publication number
CN104201370A
CN104201370A CN201410337295.1A CN201410337295A CN104201370A CN 104201370 A CN104201370 A CN 104201370A CN 201410337295 A CN201410337295 A CN 201410337295A CN 104201370 A CN104201370 A CN 104201370A
Authority
CN
China
Prior art keywords
lithium
positive electrode
preparation
nitrate
ion batteries
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410337295.1A
Other languages
Chinese (zh)
Other versions
CN104201370B (en
Inventor
陈永翀
康利斌
张艳萍
张萍
王秋平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Haofengguang Energy Storage Chengdu Co ltd
Original Assignee
BEIJING HAWAGA POWER STORAGE TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BEIJING HAWAGA POWER STORAGE TECHNOLOGY Co Ltd filed Critical BEIJING HAWAGA POWER STORAGE TECHNOLOGY Co Ltd
Priority to CN201410337295.1A priority Critical patent/CN104201370B/en
Publication of CN104201370A publication Critical patent/CN104201370A/en
Application granted granted Critical
Publication of CN104201370B publication Critical patent/CN104201370B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the technical field of electrochemical battery manufacturing, and particularly relates to a positive electrode material of a lithium ion battery, and a preparation method thereof. A general formula of the positive electrode material of the lithium ion battery is LiaMx(NiMn)yO2, and the positive electrode material has an alpha-NaFeO2 layered structure, wherein M is at least one of non-rare earth elements of Al, Mg and Cu or rare elements of La, Ce, Pr, Pm and Sm; a is equal to or larger than 1.3 as well as smaller than or equal to 1.5; x is equal to or larger than 0 as well as smaller than or equal to 0.1; and y is equal to or larger than 0.3 as well as smaller than or equal to 0.5. The preparation method of the positive electrode material has good controllability, is simple and practical, is suitable for large-scale production, has high practical degree, realizes reuse of raw materials and has high resource utilization rate.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field
The invention belongs to electrochemical cell manufacturing technology field, relate to the positive electrode using in a kind of lithium ion battery, be specifically related to a kind of positive electrode Li am x(NiMn) yo 2and preparation method thereof.
Background technology
In lithium ion battery, lithium ion is mainly derived from positive electrode, and positive electrode directly affects the energy density of lithium ion battery.In various anode material for lithium-ion batteries, what obtain widespread commercialization application is cobalt acid lithium, but the actual available specific capacity of cobalt acid lithium is 130mAhg -1, relatively on the low side, and cobalt resource is rare, and cost is higher, and this has hindered cobalt acid lithium to use on a large scale.
Consider cost and volumetric properties, nickle cobalt lithium manganate tertiary cathode material has caused to be paid close attention to widely and studies, wherein LiNi 1/3co 1/3mn 1/3o 2, LiNi 0.4co 0.2mn 0.4o 2and LiNi 0.5co 0.2mn 0.3o 2, namely often say 333,424 and 523, commercialization.Although compared with lithium cobaltate cathode material, nickle cobalt lithium manganate tertiary cathode material has reduced the cost of positive electrode to a certain extent, still contains cobalt element.
Due to the shortage of cobalt resource and the restriction of lithium cobaltate cathode material specific capacity, be necessary to research and develop specific capacity high, conduct electricity very well, have extended cycle life and not containing the positive electrode of cobalt element.For example, it is Li that the Chinese patent that publication number is 103456946A discloses a kind of expression formula 1+zni xmn ya 1-x-yo 2(0.5≤x≤0.9,0.1≤y≤0.5,0.9≤x+y≤1,0 < z≤0.1) positive electrode,, containing cobalt element, first discharge specific capacity is not greater than 130mAh/g, relatively on the low side.
Aspect method for preparing anode material, mainly contain the precipitation method, solid phase method and spray pyrolysis.The precipitation method are because the inconsistency in when precipitation makes each element ratio in finished product be difficult to accuracy controlling, and repeatability is poor; If adopt traditional solid phase method, thick, the composition of material granule and the phase lack of homogeneity of preparation; And spray pyrolysis rule spray-drying installation composition is complicated huge, investment is large, affects the many factors of product quality.
Summary of the invention
An object of the present invention is to provide a kind of positive electrode Li for lithium ion battery am x(NiMn) yo 2, positive electrode Li provided by the invention am x(NiMn) yo 2cost is low, containing cobalt element, specific capacity is high, electron conduction good, have extended cycle life.
The present invention is by the following technical solutions:
A kind of anode material for lithium-ion batteries; Described positive electrode general formula is Li am x(NiMn) yo 2, wherein M is at least one element in non-rare earth Al, Mg, Cu or rare earth element La and Ce, Pr, Pm, Sm, 1.3≤a≤1.5,0≤x≤0.1,0.3≤y≤0.5; Described positive electrode has α-NaFeO 2layer structure.
By ion doping, positive electrode electron conduction provided by the invention and cycle life effectively improve.Ion doping is to improve one of the cycle life of anode material for lithium-ion batteries and effective means of electron conduction ability.For example,, because Al-O key has stronger bond energy, therefore Al than Ni-O key and Mn-O key 3+positive electrode structure after doping is more stable, and cycle life increases; For another example, due to Cu 2+special outer-shell electron configuration, Cu 2+positive electrode electron conduction after doping can significantly be improved; The doping of other ions also can reach and the same or similar effect of above-mentioned ion.
Another object of the present invention is to provide a kind of positive electrode Li am x(NiMn) yo 2preparation method, it is characterized in that, comprise the following steps:
(a) under room temperature environment, than taking lithium nitrate, nickel nitrate, manganese nitrate and treating the nitrate of doped metal ion, the raw material taking is placed in to container by metering, adds appropriate amount of deionized water, adopt liquid phase mixed method that raw material is mixed, obtain mixed solution;
(b) mixed solution step (a) being made at a certain temperature by drum dryer evaporate, be dried, pyrolysis obtains oxides of nitrogen gas and solid precursor;
(c) step (b) gained oxides of nitrogen gas is changed into rare nitric acid through suitable processing in absorption converter, and react with lithium carbonate or lithium hydroxide, nickel hydroxide, manganese carbonate or manganous hydroxide respectively, make lithium nitrate, nickel nitrate, manganese nitrate, use in step (a) as raw material;
(d) step (b) gained solid precursor is made to powder by fragmentation;
(e) by the powder obtaining in heat treatment step (d), obtain Li am x(NiMn) yo 2positive electrode product.
As described preparation method's further improvement, in described step (a), the concentration of solution is 0.5mol/L～1.5mol/L;
As described preparation method's further improvement, described step (b) intermediate roll drier is single drum dryer, double drum dryer or multiple-roll drier;
As described preparation method's further improvement, the rotating speed of described step (b) intermediate roll is 0.1r/min～1r/min;
As described preparation method's further improvement, described step (b) intermediate roll surface temperature is 300 DEG C-600 DEG C;
As described preparation method's further improvement, in described step (d) crumbling method be grinding, ball milling or pulverize at least one;
As described preparation method's further improvement, in described step (e), heat treated temperature is 600 DEG C-900 DEG C;
As described preparation method's further improvement, in described step (e), the heat treated time is 4h-12h.
Advantage applies of the present invention exists:
(1) compare Li of the present invention with tertiary cathode material with traditional cobalt acid lithium am x(NiMn) yo 2positive electrode does not contain cobalt element, and cost is low, and environmental pollution is little;
(2) Li provided by the present invention am x(NiMn) yo 2the preparation method of positive electrode, compared with coprecipitation, its product component can accurately be controlled by the composition of nitrate solution, reproducible; Compared with conventional solid-state method, its product fine size, purity are high, mutually even, and the diffusion length of lithium ion is shortened, and have promoted deviating from and embedding of lithium ion, improve the chemical property of material; Compared with spray pyrolysis, simple, suitable for mass production, degree of being practical is high.
Brief description of the drawings
Fig. 1 is positive electrode Li of the present invention am x(NiMn) yo 2preparation method's theory diagram;
Fig. 2 is double drum dryer operation principle schematic diagram in the embodiment of the present invention one, in figure: 100-hopper, 101-leakage plate, 201-cylinder, 202-scraper, 300-collector;
Fig. 3 is Li of the present invention prepared by the embodiment of the present invention one 1.3cu 0.1ni 0.4mn 0.4o 2xRD collection of illustrative plates;
Fig. 4 is Li prepared by the embodiment of the present invention one 1.3cu 0.1ni 0.4mn 0.4o 2the first charge-discharge figure of positive electrode, first discharge specific capacity reaches 175mAh/g.
Embodiment
Describe Li of the present invention in detail below in conjunction with specific embodiment am x(NiMn) yo 2positive electrode and preparation method thereof; Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment mono-:
The positive electrode that the present embodiment provides, its expression formula is Li 1.3cu 0.1ni 0.4mn 0.4o 2.
Material preparation:
The preparation method of this positive electrode comprises the following steps:
The first step, with mol ratio 1.3:0.1:0.4:0.4, takes respectively lithium nitrate, copper nitrate, nickel nitrate, manganese nitrate, and the raw material weighing up is placed in container, adds deionized water, electric stirring, and being mixed with concentration is the stand-by solution of 0.5mol/L;
Second step, it is 300 DEG C that double drum dryer two series cylinder heating-up temperatures are set, rotating speed is 0.1r/min; The stand-by solution that the first step is prepared is transported in the hopper of drier, and the solution that enters hopper drips solution in the grooved area that is spilled into two series cylinder middle parts by the leakage plate below hopper; Along with the rotation of cylinder, the solution in grooved area is attached to two cylinder outer walls with the form of liquid film, and at 300 DEG C, liquid film evaporation, dry, pyrolysis become plate-like material to stick to cylinder outer wall; Under scraper effect, the plate-like material of cylinder outer wall unloads, and in income collector, obtains positive electrode presoma; The oxynitrides gas collection simultaneously pyrolysis being produced is to absorbing in converter;
The 3rd step, carries out crushing and classification by positive electrode presoma, obtains the particle of median particle diameter between 0.1-1 μ m;
The 4th step, the presoma powder obtaining is at 800 DEG C, and heat treatment 8h obtains positive electrode, carries out crushing and classification after product is cooling, obtains the final products Li of median particle diameter between 0.1-1 μ m 1.3cu 0.1ni 0.4mn 0.4o 2.
Structured testing:
Test the XRD spectra that obtains positive electrode powder by XRD, as shown in Figure 2, the positive electrode that embodiment mono-provides has typical α-NaFeO 2layer structure.
Performance test:
By the Li of above-mentioned preparation 1.3cu 0.1ni 0.4mn 0.4o 2material mixes according to mass ratio 85:7:8 with acetylene black conductor (commercially available) and polyvinylidene fluoride PVDF binding agent (commercially available), makes anode pole piece taking aluminium foil as collector.With the LiPF of 1mol/L 6the mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) as electrolyte, be assembled into CR2025 type button cell taking lithium metal as negative pole and carry out electrochemical property test.Discharging and recharging interval voltage is 2-4.8V, and under 0.5C multiplying power, specific discharge capacity is 175mAh/g, as shown in Figure 3.
Embodiment bis-:
The positive electrode that the present embodiment provides, its expression formula is Li 1.4al 0.05ni 0.4mn 0.4o 2.
Material preparation:
The preparation method of this positive electrode comprises the following steps:
The first step, with mol ratio 1.4:0.05:0.4:0.4, takes respectively lithium nitrate, aluminum nitrate, nickel nitrate, manganese nitrate, and the raw material weighing up is placed in container, adds deionized water, electric stirring, and being mixed with concentration is the stand-by solution of 1mol/L;
Second step, it is 400 DEG C that double drum dryer two series cylinder heating-up temperatures are set, rotating speed 0.5r/min; The stand-by solution that the first step is prepared is transported in the hopper of drier, and the solution that enters hopper drips solution in the grooved area that is spilled into two series cylinder middle parts by the leakage plate below hopper; Along with the rotation of cylinder, the solution in grooved area is attached to two cylinder outer walls with the form of liquid film, and at 400 DEG C, liquid film evaporation, dry, pyrolysis become plate-like material to stick to cylinder outer wall; Under scraper effect, the plate-like material of cylinder outer wall unloads, and in income collector, obtains positive electrode presoma; The oxynitrides gas collection simultaneously pyrolysis being produced is to absorbing in converter;
The 3rd step, carries out crushing and classification by positive electrode presoma, obtains the particle of median particle diameter between 0.1-1 μ m;
The 4th step, the presoma powder obtaining is at 900 DEG C, and heat treatment 4h obtains positive electrode, carries out crushing and classification after product is cooling, obtains the final products Li of median particle diameter between 0.1-1 μ m 1.4al 0.05ni 0.4mn 0.4o 2.
Structured testing:
Test the XRD spectra that obtains positive electrode powder by XRD, the positive electrode that provides with embodiment mono-is the same also has typical α-NaFeO 2layer structure.
Performance test:
By the Li of above-mentioned preparation 1.4al 0.05ni 0.4mn 0.4o 2material mixes according to mass ratio 85:7:8 with acetylene black conductor (commercially available) and polyvinylidene fluoride PVDF binding agent (commercially available), makes anode pole piece taking aluminium foil as collector.With the LiPF of 1mol/L 6the mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) as electrolyte, be assembled into CR2025 type button cell taking lithium metal as negative pole and carry out electrochemical property test.Discharging and recharging interval voltage is 2-4.8V, and under 0.5C multiplying power, specific discharge capacity is 181mAh/g.
Embodiment tri-:
The positive electrode that the present embodiment provides, its expression formula is Li 1.5mg 0.01ni 0.5mn 0.5o 2.
Material preparation:
The preparation method of this positive electrode comprises the following steps:
The first step, with mol ratio 1.5:0.01:0.5:0.5, takes respectively lithium nitrate, magnesium nitrate, nickel nitrate, manganese nitrate, and the raw material weighing up is placed in container, adds deionized water, electric stirring, and being mixed with concentration is the stand-by solution of 1.5mol/L;
Second step, it is 500 DEG C that bitubular drier two series cylinder heating-up temperatures are set, rotating speed 1r/min; The stand-by solution that the first step is prepared is transported in the hopper of drier, and the solution that enters hopper drips solution in the grooved area that is spilled into two series cylinder middle parts by the leakage plate below hopper; Along with the rotation of cylinder, the solution in grooved area is attached to two cylinder outer walls with the form of liquid film, and at 500 DEG C, liquid film evaporation, dry, pyrolysis become plate-like material to stick to cylinder outer wall; Under scraper effect, the plate-like material of cylinder outer wall unloads, and in income collector, obtains positive electrode presoma; The oxynitrides gas collection simultaneously pyrolysis being produced is to absorbing in converter;
The 3rd step, carries out crushing and classification by positive electrode presoma, obtains the particle of median particle diameter between 0.1-1 μ m;
The 4th step, the presoma powder obtaining is at 600 DEG C, and heat treatment 12h obtains positive electrode, carries out crushing and classification after product is cooling, obtains the final products Li of median particle diameter between 0.1-1 μ m 1.5mg 0.01ni 0.5mn 0.5o 2.
Structured testing:
Test the XRD spectra that obtains positive electrode powder by XRD, the positive electrode that provides with embodiment mono-is the same also has typical α-NaFeO 2layer structure.
Performance test:
By the Li of above-mentioned preparation 1.5mg 0.01ni 0.5mn 0.5o 2material mixes according to mass ratio 85:7:8 with acetylene black conductor (commercially available) and polyvinylidene fluoride PVDF binding agent (commercially available), makes anode pole piece taking aluminium foil as collector.With the LiPF of 1mol/L 6the mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) as electrolyte, be assembled into CR2025 type button cell taking lithium metal as negative pole and carry out electrochemical property test.Discharging and recharging interval voltage is 2-4.8V, and under 0.5C multiplying power, specific discharge capacity is 188mAh/g.
Embodiment tetra-:
The positive electrode that the present embodiment provides, its expression formula is Li 1.5la 0.005ni 0.5mn 0.5o 2.
Material preparation:
The preparation method of this positive electrode comprises the following steps:
The first step, with mol ratio 1.5:0.005:0.5:0.5, takes respectively lithium nitrate, lanthanum nitrate, nickel nitrate, manganese nitrate, and the raw material weighing up is placed in container, adds deionized water, electric stirring, and being mixed with concentration is the stand-by solution of 0.8mol/L;
Second step, it is 500 DEG C that bitubular drier two series cylinder heating-up temperatures are set, rotating speed 0.8r/min; The stand-by solution that the first step is prepared is transported in the hopper of drier, and the solution that enters hopper drips solution in the grooved area that is spilled into two series cylinder middle parts by the leakage plate below hopper; Along with the rotation of cylinder, the solution in grooved area is attached to two cylinder outer walls with the form of liquid film, and at 500 DEG C, liquid film evaporation, dry, pyrolysis become plate-like material to stick to cylinder outer wall; Under scraper effect, the plate-like material of cylinder outer wall unloads, and in income collector, obtains positive electrode presoma; The oxynitrides gas collection simultaneously pyrolysis being produced is to absorbing in converter;
The 3rd step, carries out crushing and classification by positive electrode presoma, obtains the particle of median particle diameter between 0.1-1 μ m;
The 4th step, the presoma powder obtaining is at 700 DEG C, and heat treatment 10h obtains positive electrode, carries out crushing and classification after product is cooling, obtains the final products Li of median particle diameter between 0.1-1 μ m 1.5la 0.005ni 0.5mn 0.5o 2.
Structured testing:
Test the XRD spectra that obtains positive electrode powder by XRD, the positive electrode that provides with embodiment mono-is the same also has typical α-NaFeO 2layer structure.
Performance test:
By the Li of above-mentioned preparation 1.5la 0.005ni 0.5mn 0.5o 2material mixes according to mass ratio 85:7:8 with acetylene black conductor (commercially available) and polyvinylidene fluoride PVDF binding agent (commercially available), makes anode pole piece taking aluminium foil as collector.With the LiPF of 1mol/L 6the mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) as electrolyte, be assembled into CR2025 type button cell taking lithium metal as negative pole and carry out electrochemical property test.Discharging and recharging interval voltage is 2-4.8V, and under 0.5C multiplying power, specific discharge capacity is 180mAh/g.
The specific embodiment of the invention is not in order to limit the present invention.Any those of ordinary skill in the art, do not departing from technical solution of the present invention scope situation, all can utilize method and the technology contents of above-mentioned announcement to make many possible variations and modification to technical solution of the present invention, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not depart from technical solution of the present invention,, all still belongs in the scope of technical solution of the present invention protection any simple modification made for any of the above embodiments, equivalent variations and modification according to technical spirit of the present invention.

Claims (6)

1. an anode material for lithium-ion batteries, described positive electrode has α-NaFeO 2layer structure, general formula is Li am x(NiMn) yo 2, wherein M is at least one element in non-rare earth Al, Mg, Cu or rare earth element La and Ce, Pr, Pm, Sm, 1.3≤a≤1.5,0≤x≤0.1,0.3≤y≤0.5.
2. a preparation method for anode material for lithium-ion batteries, is characterized in that, comprises the following steps:
The first step, under room temperature environment, by metering than taking lithium nitrate, nickel nitrate, manganese nitrate and treating the nitrate of doped metal ion, the raw material taking is placed in to container, add appropriate amount of deionized water, adopt liquid phase mixed method that raw material is mixed, obtain mixed solution;
Second step, the mixed solution that the first step is made at a certain temperature by drum dryer evaporate, be dried, pyrolysis obtains oxides of nitrogen gas and solid precursor;
The 3rd step, second step gained oxides of nitrogen gas is changed into rare nitric acid through suitable processing in absorption converter, and react with lithium carbonate or lithium hydroxide, nickel hydroxide, manganese carbonate or manganous hydroxide respectively, make lithium nitrate, nickel nitrate, manganese nitrate, use in second step as raw material;
The 4th step, makes powder by second step gained solid precursor by fragmentation;
The 5th step, by the powder obtaining in heat treatment the 4th step, obtains Li am x(NiMn) yo 2positive electrode product, wherein M is at least one element in non-rare earth Al, Mg, Cu or rare earth element La and Ce, Pr, Pm, Sm, 1.3≤a≤1.5,0≤x≤0.1,0.3≤y≤0.5.
3. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that: in the first step, the concentration of solution is 0.5mol/L～1.5mol/L.
4. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that: second step intermediate roll drier can be single drum dryer, double drum dryer or multiple-roll drier; The rotating speed of cylinder is 0.1r/min～1r/min; Cylinder surface temperature is 300 DEG C-600 DEG C.
5. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that: in the 4th step fragmentation be grinding, ball milling or pulverize at least one.
6. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that: in the 5th step, heat treated temperature is 600 DEG C-900 DEG C; The heat treated time is 4h-12h.
CN201410337295.1A 2014-07-16 2014-07-16 A kind of anode material for lithium-ion batteries and preparation method thereof Active CN104201370B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410337295.1A CN104201370B (en) 2014-07-16 2014-07-16 A kind of anode material for lithium-ion batteries and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410337295.1A CN104201370B (en) 2014-07-16 2014-07-16 A kind of anode material for lithium-ion batteries and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104201370A true CN104201370A (en) 2014-12-10
CN104201370B CN104201370B (en) 2016-10-05

Family

ID=52086634

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410337295.1A Active CN104201370B (en) 2014-07-16 2014-07-16 A kind of anode material for lithium-ion batteries and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104201370B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103311540A (en) * 2013-05-27 2013-09-18 华南师范大学 Lithium ion battery anode material and preparation method thereof
CN103456946A (en) * 2013-09-12 2013-12-18 刘志航 Anode material for lithium ion battery
JP2014007034A (en) * 2012-06-22 2014-01-16 Gs Yuasa Corp Active material for nonaqueous electrolyte secondary battery, electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014007034A (en) * 2012-06-22 2014-01-16 Gs Yuasa Corp Active material for nonaqueous electrolyte secondary battery, electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
CN103311540A (en) * 2013-05-27 2013-09-18 华南师范大学 Lithium ion battery anode material and preparation method thereof
CN103456946A (en) * 2013-09-12 2013-12-18 刘志航 Anode material for lithium ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
封志芳: "稀土La3+、Ce3+掺杂Li[Li(1-2x)/3NixMn(2-x)/3]O2材料的电化学性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅱ辑》, no. 11, 15 November 2011 (2011-11-15) *
张绍丽: "锂镍锰复合氧化物正极材料的制备与掺杂改性研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅱ辑》, no. 04, 15 December 2004 (2004-12-15) *

Also Published As

Publication number Publication date
CN104201370B (en) 2016-10-05

Similar Documents

Publication Publication Date Title
CN102790217B (en) Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof
Tang et al. Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2
CN102044671B (en) Spinel type lithium manganate electrode material and preparation method thereof
CN102263239B (en) One kind graphene coated adulterated lithium manganate composite positive pole and preparation method thereof
CN102544481B (en) Lithium ion battery and cathode material thereof
CN107275606B (en) Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof
CN103972499B (en) A kind of nickel cobalt lithium aluminate cathode material of modification and preparation method thereof
CN101771145B (en) Method for preparing multielement cathode materials for lithium ion batteries
CN102437323A (en) Anode material of lithium ion battery and preparation method thereof
CN103094550A (en) Preparation method of lithium-rich anode material
CN104681816A (en) Lithium-manganese-oxide-based positive electrode active material and preparation method thereof
CN108550802A (en) A kind of nickel-cobalt-manganternary ternary anode material and preparation method that Y/La doping Co/B is coated altogether
CN108493435A (en) Anode material for lithium-ion batteries Li (Ni0.8Co0.1Mn0.1)1-xYxO2And preparation method
CN103078099A (en) Anode material for lithium ion cell and preparation method thereof
CN105006574A (en) Surface-modified anode material for lithium ion battery and preparation method thereof
Zhang et al. Optimizing Li2O-2B2O3 coating layer on LiNi0. 8Co0. 1Mn0. 1O2 (NCM811) cathode material for high-performance lithium-ion batteries
CN106935830A (en) A kind of lithium ion battery composite cathode material and its preparation method and application
CN103035904A (en) Modified lithium manganate material, and preparation method and application thereof
Li et al. Synthesis and properties of nanostructured LiNi1/3Co1/3Mn1/3O2 as cathode with lithium bis (oxalate) borate-based electrolyte to improve cycle performance in Li-ion battery
CN103187566B (en) Tubular lithium-rich anode material, preparation method and application thereof
CN106784657A (en) A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material
Jia et al. Improving the rate performance of LiNi 0.5 Mn 0.5 O 2 material at high voltages by Cu-doping
CN105895906A (en) Lithium-doped ternary lithium-ion battery positive electrode material and preparation method thereof
CN103268939A (en) Preparation method of lithium ferrous silicate anode composite material
CN102522564A (en) Rheological phase method for preparing sodium-doped positive pole material lithium vanadium phosphate of lithium-ion battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP03 Change of name, title or address

Address after: No. 1, 1st Floor, Building 4, No. 10, South 3rd Road, Shodu, Wuhou District, Chengdu City, Sichuan Province, 610043

Patentee after: Haofengguang Energy storage (Chengdu) Co.,Ltd.

Address before: 1711, 17th floor, building 2, yard 1, Shangdi 10th Street, Haidian District, Beijing 100085

Patentee before: Beijing Hawaga Power Storage Technology Co.,Ltd.

CP03 Change of name, title or address