CN110323432A - A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof - Google Patents

A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof Download PDF

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CN110323432A
CN110323432A CN201910620561.4A CN201910620561A CN110323432A CN 110323432 A CN110323432 A CN 110323432A CN 201910620561 A CN201910620561 A CN 201910620561A CN 110323432 A CN110323432 A CN 110323432A
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lithium
doping
anion
cation
ion battery
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杨书廷
王科
王明阳
尚啸坤
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Henan Battery Research Institute Co Ltd
Henan Normal University
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Henan Battery Research Institute Co Ltd
Henan Normal University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses miscellaneous modification lithium-ion battery anode materials of a kind of cation-anion co-doping and preparation method thereof, belong to the preparation technical field of lithium-enriched cathodic material of lithium ion battery.Technical solution of the present invention main points are as follows: a kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping, chemical formula Li1.2Mn0.54Ni0.16Co0.1‑ xAlxO2‑yFy, wherein 0 < x≤0.05,0 y≤0.05 <.The invention further particularly discloses the preparation methods of the miscellaneous modification lithium-ion battery anode material of the cation-anion co-doping, the anode material for lithium-ion batteries surface prepared using this method is smooth, and particle is uniform, and structural strength is high, tap density is big, shows excellent chemical property.Lithium-rich oxide material prepared by the present invention, since primary particle is nano particle, biggish specific surface area is conducive to the deintercalation of lithium ion in cyclic process, increases coming into full contact with for electrolyte and material, improves the capacity and cycle performance of material.

Description

A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof
Technical field
The invention belongs to the preparation technical fields of lithium-enriched cathodic material of lithium ion battery, and in particular to a kind of zwitterion is total Doped modified lithium ion battery anode material and preparation method thereof.
Background technique
In recent years, as people's environmental consciousness significantly increases, lithium ion battery is being developed rapidly, especially in electronic vapour Vehicle and energy-storage system field.It is widely applied to pursue lithium ion battery, energy density must further increase, so Numerous researchers are dedicated to developing a kind of new anode material for lithium-ion batteries.In numerous positive electrodes, lithium-rich oxygen Compound material is had great expectations with the advantage of its high capacity by people.Traditional positive electrode capacity is generally 100-150mAh/ G, and this its capacity of lithium-rich oxide anode material is up to 250mAh/g, significantly larger than traditional lithium ion cell positive Material.But with the progress of charge and discharge cycles, the reversible capacity of this lithium-rich oxide material can quickly decay, In addition, at room temperature, the irreversible capacity for the first time of the material reaches 20% or more, the monomer of this lithium ion battery undoubtedly reduced Energy density.In order to use the lithium-rich oxide anode material the energy density that improves lithium ion battery, people are positive Searching means are modified the cycle performance and irreversible capacity of the material.
Now, Most scholars think that lithium-rich oxide material is by Li2MnO3And LiMO2(wherein M be Mn, Ni or One or more of Co) solid solution that is collectively formed, wherein Li2MnO3For monoclinic system, LiMO2For hexagonal crystal system.In head In secondary cyclic process, when charging voltage is greater than 4.5V, Li2MnO3Start to activate, a large amount of Li+Deviate from from structure, and has O2It releases It puts;And in discharge process for the first time, due to O2It is irreversible, so only 50% or so Li+It can be embedded into structure again, from And cause lithium-rich oxide material head effect lower.In addition, spinel structure is that thermodynamics is steady due in manganese-based compound Phase is determined, so layer structure gradually changes to spinel structure with the progress of charge and discharge cycles.
The disadvantages of low, high rate performance is poor based on lithium-rich oxide material head effect, people are usually used to be coated, is male/female The means such as ion doping improve the chemical property of the material, to improve the energy density of lithium ion battery, accelerate the material The commercialization process of material.
Summary of the invention
The present invention is to overcome the shortcomings of the prior art, effectively solves lithium-rich oxide material inside configuration and stablizes Property difference problem, a kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof is provided, using this The anode material for lithium-ion batteries surface of method preparation is smooth, and particle is uniform, and structural strength is high, and tap density is big, shows excellent Different chemical property.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of miscellaneous modification lithium-ion of cation-anion co-doping Cell positive material, it is characterised in that the chemical formula of the miscellaneous modification lithium-ion battery anode material of the cation-anion co-doping is Li1.2Mn0.54Ni0.16Co0.1-xAlxO2-yFy, wherein 0 < x≤0.05,0 y≤0.05 <.
The preparation method of the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping of the present invention, it is characterised in that Specific steps are as follows:
Step S1: mixed metal salt is prepared by raw material of soluble manganese salt, soluble nickel salt, soluble cobalt and aluminum soluble salt Solution, wherein metal ion total mol concentration is 1 ~ 3mol/L;
Step S2: compound concentration be 1 ~ 10mol/L aqueous slkali be used as precipitating reagent, wherein alkali be sodium hydroxide, potassium hydroxide or One of rubidium hydroxide is a variety of;
Step S3: the ammonia spirit that mass concentration is 2% ~ 20% is prepared as complexing agent;
Step S4: mixed salt solution, precipitating reagent and complexing agent are added to inert gas shielding atmosphere by precision metering pump Reaction kettle in carry out coprecipitation reaction, control stirring rate is 200 ~ 1000rpm/min and maintains mixed salt solution Flow velocity is constant, and the flow velocity by adjusting precipitating reagent and complexing agent maintains pH=9 ~ 14 of reaction system, and control reaction temperature is 30 ~ 60 DEG C, it is aged 2 ~ 16h after reaction, by product washing, is dried to obtain lithium-rich oxide precursor;
Step S5: lithium-rich oxide precursor is mixed with lithium source and LiF according to the stoichiometric ratio of target product, wherein Lithium source is one of lithium carbonate or lithium hydroxide or a variety of, is first warming up to 300 ~ 500 DEG C in advance with the heating rate of 1 ~ 5 DEG C/min It is sintered 4 ~ 8h, then 700 ~ 950 DEG C of 12 ~ 18h of sintering are warming up to the heating rate of 3 ~ 8 DEG C/min, sieve is taken out in then furnace cooling Get the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping.
Preferably, solubility manganese salt described in step S1 is one of manganese sulfate, manganese nitrate or manganese chloride or a variety of;Institute Stating soluble nickel salt is one of nickel sulfate, nickel nitrate or nickel chloride or a variety of;The soluble cobalt is cobaltous sulfate, nitric acid One of cobalt or cobalt chloride are a variety of;The aluminum soluble salt is one of aluminum sulfate, aluminum nitrate or aluminium chloride or a variety of.
Preferably, the molar concentration of precipitating reagent described in step S2 is 3 ~ 7mol/L.
Preferably, the mass concentration of complexing agent described in step S3 is 8% ~ 15%.
Preferably, stirring rate is controlled in step S4 to be 200 ~ 500rpm/min and maintain the flow velocity of mixed salt solution Constant, the flow velocity by adjusting precipitating reagent and complexing agent maintains pH=10 ~ 12 of reaction system, and control reaction temperature is 45 ~ 55 DEG C, it is aged 8 ~ 12h after reaction.
Preferably, hybrid mode is that wet-mixing, dry mixed or clipping the ball are one of mixed or a variety of in step S5.
Compared with the prior art, the invention has the following beneficial effects:
1, the present invention is during using coprecipitation preparation lithium-rich manganese base material presoma, by controlling various process parameters Presoma primary particle pattern obtained is in nano-sheet, increases the specific surface area of material;Second particle surface is smooth, structure Densification improves the stability of material;
2, lithium-rich oxide material prepared by the present invention, due to cation A l3+Introducing, can be with the inside of stabilizing material Structure inhibits material to change to spinel structure, reduces the decaying of voltage, improve the cyclicity of material as the cycle progresses Energy and high rate performance;Anion F-Introducing reduced in cyclic process for the first time instead of the position of intracell part O O2Release, to improve the first effect of material;
3, lithium-rich oxide material prepared by the present invention, since primary particle is nano particle, biggish specific surface area has Conducive to the deintercalation of lithium ion in cyclic process, increases coming into full contact with for electrolyte and material, improve the capacity and circulation of material Performance;
4, the whole flow process simple process of present invention preparation lithium-rich oxide material, and it is easily achieved extensive automatic chemical industry Industry production.
Detailed description of the invention
Fig. 1 is the XRD diagram that lithium-rich oxide is made in different embodiments of the invention, and wherein a is richness prepared by embodiment 1 Lithium layered oxide Li1.2Mn0.54Ni0.16Co0.1O2XRD diagram, b be embodiment 6 prepare lithium-rich oxide Li1.2 Mn0.54Ni0.16Co0.07Al0.03O1.97F0.03XRD diagram;
Fig. 2 is the SEM figure that lithium-rich oxide is made in different embodiments of the invention, and wherein a is rich lithium layer prepared by embodiment 1 Shape oxide Li1.2Mn0.54Ni0.16Co0.1O2SEM figure, b be embodiment 6 prepare lithium-rich oxide Li1.2Mn0.54 Ni0.16Co0.07Al0.03O1.97F0.03SEM figure;
A and b is respectively the lithium-rich oxide prepared in the embodiment of the present invention 1 and embodiment 6 in Fig. 3 Li1.2Mn0.54Ni0.16Co0.1O2And Li1.2Mn0.54Ni0.16Co0.07Al0.03O1.97F0.03The charge and discharge for the first time at 0.1C, 2.1 ~ 4.8V Electric curve graph;
A and b is respectively the lithium-rich oxide prepared in the embodiment of the present invention 1 and embodiment 6 in Fig. 4 Li1.2Mn0.54Ni0.16Co0.1O2And Li1.2Mn0.54Ni0.16Co0.07Al0.03O1.97F0.03It is 2.1 ~ 4.8V, electric current in voltage range Cycle life curve figure when density is 1C.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Embodiment 1
(1) the mixing gold of manganese sulfate, nickel sulfate and cobaltous sulfate is prepared according to stoichiometric ratio Mn:Ni:Co=0.54:0.16:0.1 Belong to salting liquid, wherein metal ion total concentration is 2mol/L;Compound concentration is the sodium hydroxide solution of 6mol/L;It is dense to prepare quality The ammonia spirit that degree is 12%;
(2) solution that above-mentioned 3 kinds are prepared is added in continuous stirred tank reactor simultaneously, nitrogen protection is remained in fill process Atmosphere simultaneously maintains mixed salt solution flow velocity constant, and the flow velocity by adjusting sodium hydroxide solution and ammonia spirit maintains reaction PH=11.5 of system, control reaction temperature are 50 DEG C, stirring rate 400rpm/min, continue stirring ageing after reaction 10h by reaction product washing, is dried to obtain lithium-rich oxide precursor;
It (3) is to mix according to molar ratio Li:Me=1.25:0.8(Me with lithium carbonate by obtained lithium-rich oxide precursor Metal ion total mole number in salting liquid, lithium source is excessive 5%), and dry mixed is uniform in a high speed mixer, is placed in crucible, It is calcined in air atmosphere stove, be warming up to 400 DEG C first with the heating rate of 3 DEG C/min and keep the temperature 5h, then with the heating of 5 DEG C/min Rate is warming up to 900 DEG C and keeps the temperature 15h, last furnace cooling, takes out sieving and obtains lithium-rich oxide anode material Li1.2Mn0.54Ni0.16Co0.1O2
Embodiment 2
The present embodiment is specific as follows the difference from embodiment 1 is that material mol ratio is different in (1) step:
Manganese sulfate, nickel sulfate, cobaltous sulfate and sulphur are prepared according to stoichiometric ratio Mn:Ni:Co:Al=0.54:0.16:0.09:0.01 The mixed salt solution of sour aluminium, metal ion total concentration are 2mol/L;Compound concentration is the sodium hydroxide solution of 6mol/L;Match The ammonia spirit that mass concentration processed is 12%.
Finally obtain lithium-rich oxide anode material Li1.2Mn0.54Ni0.16Co0.09Al0.01O2
Embodiment 3
The present embodiment is specific as follows the difference from embodiment 1 is that material mol ratio is different in (1) step:
Manganese sulfate, nickel sulfate, cobaltous sulfate and sulphur are prepared according to stoichiometric ratio Mn:Ni:Co:Al=0.54:0.16:0.07:0.03 The mixed salt solution of sour aluminium, metal ion total concentration are 2mol/L;Compound concentration is the sodium hydroxide solution of 6mol/L;Match The ammonia spirit that mass concentration processed is 12%.
Finally obtain lithium-rich oxide anode material Li1.2Mn0.54Ni0.16Co0.07Al0.03O2
Embodiment 4
The present embodiment is specific as follows the difference from embodiment 1 is that material mol ratio is different in (1) step:
Manganese sulfate, nickel sulfate, cobaltous sulfate and sulphur are prepared according to stoichiometric ratio Mn:Ni:Co:Al=0.54:0.16:0.05:0.05 The mixed salt solution of sour aluminium, metal ion total concentration are 2mol/L;Compound concentration is the sodium hydroxide solution of 6mol/L;Match The ammonia spirit that mass concentration processed is 12%.
Finally obtain lithium-rich oxide anode material Li1.2Mn0.54Ni0.16Co0.05Al0.05O2
Embodiment 5
(1) manganese sulfate, nickel sulfate, cobaltous sulfate are prepared according to stoichiometric ratio Mn:Ni:Co:Al=0.54:0.16:0.07:0.03 With the mixed salt solution of aluminum sulfate, metal ion total concentration is 2mol/L;Compound concentration is that the sodium hydroxide of 6mol/L is molten Liquid;Prepare the ammonia spirit that mass concentration is 12%;
(2) solution that above-mentioned 3 kinds are prepared is added in continuous stirred tank reactor simultaneously, nitrogen protection is remained in fill process Atmosphere simultaneously maintains mixing salt solution flow velocity constant, and the flow velocity by adjusting sodium hydroxide solution and ammonia spirit maintains reaction system PH=11.5, control reaction temperature be 50 DEG C, stirring rate 400rpm/min, continue after reaction stirring ageing 10h, By reaction product washing, it is dried to obtain lithium-rich oxide precursor;
(3) by lithium carbonate and lithium-rich oxide precursor and LiF according to molar ratio Li:Me:LiF=1.24:0.8:0.01 (Me is metal ion total mole number in mixing salt solution, and lithium source is excessive 5%), and dry mixed is uniform in a high speed mixer, is placed in In crucible, calcined in air atmosphere stove, be warming up to 400 DEG C first with the heating rate of 3 DEG C/min and keep the temperature 5h, then with 5 DEG C/ The heating rate of min is warming up to 900 DEG C and keeps the temperature 15h, last furnace cooling, takes out sieving and obtains lithium-rich oxide anode Material Li1.2Mn0.54Ni0.16Co0.07Al0.03O1.99F0.01
Embodiment 6
The present embodiment is in (3) step that material mol ratio is different from the difference of embodiment 5, specific as follows:
By lithium carbonate and lithium-rich oxide precursor and LiF according to molar ratio Li:Me:LiF=1.22:0.8:0.03(Me For metal ion total mole number in mixing salt solution, lithium source excess is 5%).
Finally obtain lithium-rich oxide anode material Li1.2Mn0.54Ni0.16Co0.07Al0.03O1.97F0.03
Embodiment 7
The present embodiment is in (3) step that material mol ratio is different from the difference of embodiment 5, specific as follows:
By lithium carbonate and lithium-rich oxide precursor and LiF according to molar ratio Li:Me:LiF=1.2:0.8:0.05(Me For metal ion total mole number in mixing salt solution, lithium source excess is 5%).
Finally obtain lithium-rich oxide anode material Li1.2Mn0.54Ni0.16Co0.07Al0.03O1.95F0.05
Application Example
The lithium-rich oxide anode material that each embodiment is obtained is respectively with conductive agent carbon black, binder PVDF according to matter Amount uniformly, adds appropriate NMP and is tuned into slurry, be evenly coated on pretreated aluminium foil, in air dry oven than 8:1:1 grinding In 80 DEG C of dry 1h, then 110 DEG C of dry 12h in a vacuum drying oven;Round positive plate is fabricated to slitter later.With the pole Piece is anode, and metal lithium sheet is cathode, the LiPF of 1mol/L6(EC:DMC=1:1) is electrolyte, in the glove box for being full of argon gas 2032 type button cells of interior assembly.It is to test the chemical property of the material in 2.1 ~ 4.8V in voltage range.
XRD diagram shown in FIG. 1 can be seen that two kinds of materials all have α-NaFeO2Layer structure, diffraction maximum is sharp, division Obviously, without other obvious impurity peaks;Scheme b Li between 20 ~ 22 °2MnO3Characteristic peak it is obvious, illustrate to pass through cation-anion co-doping Miscellaneous modification can be with the internal structure of stabilizing material, the stability of reinforcing material.
SEM figure shown in Fig. 2 is it can be seen that two kinds of material primary particle patterns are in flaky nanometer structure, second particle table Face is smooth, compact structure;Obviously become larger it can be seen from (b) by primary particle of the cation-anion co-doping after miscellaneous in figure.
First charge-discharge curve shown in Fig. 3 can be seen that the lithium-rich oxide anode material of the preparation of embodiment 1 Li1.2Mn0.54Ni0.16Co0.1O2(curve a) at 2.1 ~ 4.8V, first discharge specific capacity 231mAh/g, coulombic efficiency for the first time It is 78.3%;Lithium-rich oxide anode material Li prepared by embodiment 61.2Mn0.54Ni0.16Co0.07Al0.03O1.97F0.03It is (bent Line b) is at 2.1 ~ 4.8V, first discharge specific capacity 261.5mAh/g, and coulombic efficiency is 83.7% for the first time, for the first time coulombic efficiency It significantly improves.
Two kinds of materials shown in Fig. 4 when voltage range is 2.1 ~ 4.8V, and current density is 1C Li1.2Mn0.54Ni0.16Co0.1O2(curve a) and Li1.2Mn0.54Ni0.16Co0.07Al0.03O1.97F0.03(cycle life of curve b) is bent Line chart.As seen from the figure, by the lithium-ion electric of the miscellaneous modified anode material for lithium-ion batteries preparation of cation-anion co-doping Pond is after 50 circulations, capacity retention ratio 99.5%, better than undoped with modified 96.9%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (7)

1. a kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping, it is characterised in that the miscellaneous modification of the cation-anion co-doping The chemical formula of anode material for lithium-ion batteries is Li1.2Mn0.54Ni0.16Co0.1-xAlxO2-yFy, wherein 0 < x≤0.05,0 < y≤ 0.05。
2. a kind of preparation method of the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping described in claim 1, special Sign is specific steps are as follows:
Step S1: mixed metal salt is prepared by raw material of soluble manganese salt, soluble nickel salt, soluble cobalt and aluminum soluble salt Solution, wherein metal ion total mol concentration is 1 ~ 3mol/L;
Step S2: compound concentration be 1 ~ 10mol/L aqueous slkali be used as precipitating reagent, wherein alkali be sodium hydroxide, potassium hydroxide or One of rubidium hydroxide is a variety of;
Step S3: the ammonia spirit that mass concentration is 2% ~ 20% is prepared as complexing agent;
Step S4: mixed salt solution, precipitating reagent and complexing agent are added to inert gas shielding atmosphere by precision metering pump Reaction kettle in carry out coprecipitation reaction, control stirring rate is 200 ~ 1000rpm/min and maintains mixed salt solution Flow velocity is constant, and the flow velocity by adjusting precipitating reagent and complexing agent maintains pH=9 ~ 14 of reaction system, and control reaction temperature is 30 ~ 60 DEG C, it is aged 2 ~ 16h after reaction, by product washing, is dried to obtain lithium-rich oxide precursor;
Step S5: lithium-rich oxide precursor is mixed with lithium source and LiF according to the stoichiometric ratio of target product, wherein Lithium source is one of lithium carbonate or lithium hydroxide or a variety of, is first warming up to 300 ~ 500 DEG C in advance with the heating rate of 1 ~ 5 DEG C/min It is sintered 4 ~ 8h, then 700 ~ 950 DEG C of 12 ~ 18h of sintering are warming up to the heating rate of 3 ~ 8 DEG C/min, sieve is taken out in then furnace cooling Get the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping.
3. the preparation method of the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping according to claim 2, special Sign is: solubility manganese salt described in step S1 is one of manganese sulfate, manganese nitrate or manganese chloride or a variety of;The solubility Nickel salt is one of nickel sulfate, nickel nitrate or nickel chloride or a variety of;The soluble cobalt is cobaltous sulfate, cobalt nitrate or chlorination One of cobalt is a variety of;The aluminum soluble salt is one of aluminum sulfate, aluminum nitrate or aluminium chloride or a variety of.
4. the preparation method of the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping according to claim 2, special Sign is: the molar concentration of precipitating reagent described in step S2 is 3 ~ 7mol/L.
5. the preparation method of the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping according to claim 2, special Sign is: the mass concentration of complexing agent described in step S3 is 8% ~ 15%.
6. the preparation method of the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping according to claim 2, special Sign is: controlling stirring rate in step S4 and is 200 ~ 500rpm/min and maintains the flow velocity of mixed salt solution constant, leads to PH=10 ~ 12 of the flow velocity maintenance reaction system of precipitating reagent and complexing agent are overregulated, control reaction temperature is 45 ~ 55 DEG C, reaction knot 8 ~ 12h is aged after beam.
7. the preparation method of the miscellaneous modification lithium-ion battery anode material of cation-anion co-doping according to claim 2, special Sign is: hybrid mode is that wet-mixing, dry mixed or clipping the ball are one of mixed or a variety of in step S5.
CN201910620561.4A 2019-07-10 2019-07-10 A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof Pending CN110323432A (en)

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CN111584875A (en) * 2020-05-29 2020-08-25 昆山宝创新能源科技有限公司 Graphene-coated and anion-cation co-doped ternary cathode material and preparation method and application thereof
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CN113299906A (en) * 2021-05-26 2021-08-24 中南大学 Cation and fluorine anion double-doped modified ternary cathode material and preparation method thereof

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CN113299906A (en) * 2021-05-26 2021-08-24 中南大学 Cation and fluorine anion double-doped modified ternary cathode material and preparation method thereof

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