CN102790209A - Positive pole material of lithium ion battery and preparation method thereof - Google Patents
Positive pole material of lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides a positive pole material of a lithium ion battery. The positive pole material of a lithium ion battery comprises a compound having a general formula of Li1+xMXdeltaOepsilon-delta, wherein M represents at least one of Ni, Co and Mn; X represents at least one of F, Cl, Br, I and S; x is greater than 0 and less than or equal to 0.33; delta is greater than 0 and less than or equal to 0.2; and epsilon is greater than 0 and less than or equal to 10. The positive pole material of a lithium ion battery is prepared by mixing anions as dopants and transition metal oxides, improves charging-discharging voltage, rate charging-discharging performances and cycling stability, reduces a cost, and is suitable for large-scale industrial production. The invention also provides a preparation method of the positive pole material of a lithium ion battery.
Description
Technical field
The present invention relates to cell positive material and preparation field thereof, relate in particular to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
The 21st century sustainable development of human society is faced with numerous challenges, and shortage of energy sources even exhaustion possibly be wherein thorny one.For the reserves that solve human society and the energy growing to the demands for energy contradiction between the exhaustion day by day, people's exigence finds a kind of novel, cheap, energy storage efficiency is high, environment amenable battery material.In numerous battery materials; Lithium rechargeable battery is high with its voltage, outstanding advantages such as energy density is big, good cycle are considered to solve the key technology of the energy problem that possibly face human future; And the exploitation of anode material for lithium-ion batteries is the important component part of lithium ion battery technical research, and the quality of its performance can have influence on the performance of lithium ion battery performance to a great extent.The same with other materials, long evolution has also been experienced in the research and development of anode material for lithium-ion batteries.The anode material for lithium-ion batteries of commercially producing the earliest is a stratiform cobalt acid lithium.Though this positive electrode has been obtained certain success, the subject matter that cobalt acid reason material exists is: cost is too high, be prone to environment damage, thermal stability is relatively poor, fail safe is bad etc.Therefore, people constantly explore, develop new anode material for lithium-ion batteries when improving cobalt acid reason material property.
At present to be mainly transition metal oxide be that in transiting metal nickel, manganese, the cobalt one or more replace the cobalt atom in the cobalt acid reason wholly or in part to the more anode material for lithium-ion batteries of research.Wherein study more transition metal oxide material and mainly contain following series: LiMn2O4 series comprises lithium manganate having spinel structure material and layered lithium manganate material (Journal of Power Sources 51 (1994): 79.); Lithium nickelate series is like LiNi
0.8Co
0.2O
2Nickel LiMn2O4 series is like spinel-type nickel LiMn2O4 LiNi
0.5Mn
1.5O
4(Journal of the Electrochemical Society 144 (1997): 205.); Nickel cobalt manganese series is like the rich lithium-nickel-manganese-cobalt acid of stratiform lithium material.Modification work to above-mentioned series material also has many bibliographical informations, discloses a kind of nickel-manganese-cobalt positive polar material that utilizes the tin dope modification like Chinese patent CN200610012015.5; And one piece the summary type scientific paper in system introduction the method for modifying of spinel-type nickel lithium manganate material (Journal of Power Sources 195 (2010): 5442.).
But the experiment route that the transition metal oxide positive electrode is carried out modification mainly concentrates on the doping that utilizes metal cation and the coating of metal oxide improves the rate charge-discharge performance of material and the cycle performance under the hot conditions.With respect to metal cation and metal oxide; Anion is bigger at the content of occurring in nature; Obtain more easily,, can improve charging/discharging voltage, rate charge-discharge performance, stable cycle performance so the inventor considers a kind of anion doped transition metal oxide positive electrode is provided; Prodigiosin reduces cost again, is fit to large-scale industrial production.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of anode material for lithium-ion batteries and preparation method thereof; The prior art of comparing; Use anion doped preparation positive electrode, the transition metal oxide positive electrode that charging/discharging voltage is higher, the rate charge-discharge performance is more excellent, cycle performance is more stable.
In order to solve the prior art problem, the invention provides a kind of anode material for lithium-ion batteries, comprise that general formula is Li
1+xMX
δO
ε-δCompound; Wherein M is one or more among Ni, Co, the Mn; X is one or more among F, Cl, Br, I and the S; 0＜x≤0.33,0＜δ≤0.2,0＜ε≤10.
Preferably, said M is Ni
αCo
βMn
γ, 0＜α≤1,0＜β≤1,0＜γ≤1.
The present invention also provides a kind of preparation method of anode material for lithium-ion batteries, comprising:
A) Li source compound, the compound that contains M, the compound that contains X and additive are mixed, obtain mixture;
B) mixture that step a) is obtained is heat-treated, sintering, and obtaining general formula is Li
1+xMX
δO
ε-δAnode material for lithium-ion batteries; Wherein M is one or more among Ni, Co, the Mn; X is one or more among F, Cl, Br, I and the S; 0＜x≤0.33,0＜δ≤0.2,0＜ε≤10.
Preferably, said Li source compound is one or more in hydroxide, oxide, sulfate, carbonate, nitrate and the acetate of lithium.
Preferably; The compound of the said M of containing is hydroxide, oxide, sulfate, carbonate, the nitrate of nickel; The hydroxide of manganese, oxide or sulfate, carbonate, nitrate, one or more in the hydroxide of cobalt, oxide or sulfate, carbonate and the nitrate.
Preferably, the compound of the said X of containing is the compound that contains F, Cl, Br, I and S.
Preferably, said additive is one or more in oxalic acid, ammoniacal liquor, sodium carbonate, potash, NaOH, potassium hydroxide, neopelex, the citric acid.
Preferably, said additive amount accounts for the 10wt%～50wt% of mixture gross mass.
Preferably, step a) is specially:
A1) a1) that Li source compound, the compound that contains M, the compound that contains X and additive is soluble in water, obtain mixed solution;
A2) said mixed solution is dry, obtain mixture.
Preferably, step b) is specially:
B1) mixture that step a) is obtained is being heated to 500～550 ℃ from room temperature;
B2) with step b1) mixture that obtains is heated to 750～1000 ℃;
B3) with step b2) mixture that obtains is 500～800 ℃ of annealing down, obtains anode material for lithium-ion batteries.
The invention provides a kind of anode material for lithium-ion batteries, it is characterized in that, comprise that general formula is Li
1+xMX
δO
ε-δCompound; Wherein M is one or more among Ni, Co, the Mn; X is one or more among F, Cl, Br, I and the S; 0＜x≤0.33,0＜δ≤0.2,0＜ε≤10.The prior art of comparing; The present invention is added on anion in the positive electrode; Because the material crystals structural change after the anion doped modification is little; The binding force that lithium ion receives in crystal field reduces, thereby causes fast, the conductance raising of material modified middle lithium ion diffusion velocity, thereby has improved charging/discharging voltage, rate charge-discharge performance, cycle performance.In addition, it is bigger than metal cation and metal oxide at occurring in nature content to contain above-mentioned anionic compound, and price is relatively low honest and clean, so use anion doped positive electrode can reduce the cost of lithium ion battery.
The present invention also provides a kind of preparation method of anode material for lithium-ion batteries, comprising: a) Li source compound, the compound that contains M, the compound that contains X and additive are mixed, obtain mixture; B) mixture that step a) is obtained is heat-treated, sintering, and obtaining general formula is Li
1+xMX
δO
ε-δAnode material for lithium-ion batteries; Wherein M is one or more among Ni, Co, the Mn; X is one or more among F, Cl, Br, I and the S; 0＜x≤0.33,0＜δ≤0.2,0＜ε≤10.Preparation method's mild condition provided by the invention, in positive electrode, method is simple with anion doped, is fit to large-scale industrial production.
Description of drawings
Fig. 1 is embodiment 1 gained LiNi
0.5Mn
1.5O
3.95Br
0.05XRD figure;
Fig. 2 is embodiment 1 gained LiNi
0.5Mn
1.5O
3.95Br
0.05SEM figure;
Fig. 3 is gained bromine Li doped Ni among the embodiment 2
0.5Mn
1.5O
3.99Br
0.01With undoped LiNi
0.5Mn
1.5O
4The cycle performance of material relatively.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The invention provides a kind of anode material for lithium-ion batteries and comprise that general formula is Li
1+xMX
δO
ε-δCompound; Wherein M is one or more among Ni, Co, the Mn; X is one or more among F, Cl, Br, I and the S; 0≤x≤0.33,0≤δ≤0.2,0≤ε≤10.
According to the present invention, M is a transition metal in the said general formula, and said transition metal can be subgroup element, the 8th family's element or group of the lanthanides or actinide metals.The present invention uses one or more among Ni, Co, the Mn, is preferably general formula Ni
αCo
βMn
γWherein 0≤α≤1,0≤β≤1,0≤γ≤1, and α, β, γ are not zero simultaneously.
According to the present invention, said X is the anion that is entrained in the transition metal oxide, and X is one or more among F, Cl, Br, I and the S.Because the material crystals structure generation minor variations after the anion doped modification, the binding force that lithium ion receives in crystal field reduces, thereby causes material modified middle lithium ion diffusion, conductance to improve, and then improves the relevant chemical property of material.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, comprising: a) Li source compound, the compound that contains M, the compound that contains X and additive are mixed;
B) the mixture heat treatment that step a) is obtained obtains spinel-type and pinches manganate cathode material for lithium; Said heat treated mode of heating is that microwave sintering or microwave sintering and resistance heating are shared.
Preparation method provided by the invention at first mixes Li source compound, the compound that contains M, the compound that contains X and additive.According to the present invention, said Li source compound is preferably one or more in hydroxide, oxide, sulfate, carbonate, nitrate and the acetate of lithium, more preferably in lithium hydroxide, lithium acetate, the nitric acid.The compound of the said M of containing is preferably hydroxide, oxide, sulfate, carbonate, the nitrate of nickel.The hydroxide of acetate manganese, oxide, sulfate, carbonate, nitrate, acetate, one or more in the hydroxide of cobalt, oxide or sulfate, carbonate, the nitrate.More preferably manganese acetate, manganese nitrate, nickel acetate, nickel nitrate, nickelous sulfate.
The compound that contains X be contain, in the compound of Cl, Br, I and S one or more, be preferably LiF, LiCl, LiBr, LiI, Li2S, most preferably be LiBr.
Additive provided by the invention is preferably one or more in oxalic acid, ammoniacal liquor, sodium carbonate, potash, NaOH, potassium hydroxide, neopelex, the citric acid.Additive is in order to regulate pH value to 7～8 of mixture.Account for 10～50% of mixture gross mass according to content of additive according to the invention.
According to the present invention; Li source compound, the compound that contains M, the compound that contains X and additive mix and can mix through in mechanical lapping, agitation grinding, rotation stirring, vibratory milling, high energy dry ball milling, the high energy wet ball grinding one or more; If said mixture is a solid; Be to mix at 0.505～1.01: 0.5: 0.01～1.5: 2.5～3 in molar ratio preferably with Li source compound, the compound that contains M, the compound and the additive that contain X, even through ball mill mixing then.Can also with the solid Li source compound, contain M compound, contain the compound formation even mixed solution soluble in water of X, more said mixed solution is carried out drying.Also can Li source compound be provided directly, contain M compound, contain the aqueous solution of the compound of X, with the aqueous solution of additive, obtain mixed solution and more said mixed solution carried out drying then, obtain mixture.In addition, can also be earlier Li source compound, the compound that contains M, the compound that contains X be become precursor, make Li source compound, contain the compound of M, the compound that contains X evenly mixes.
According to the present invention, the mode of said drying can be in vacuum evaporation, rotary evaporation, spray drying, the freeze drying one or more, and the method for preparing precursor can be in collosol and gel, coprecipitation, the hydro thermal method one or more.
According to the present invention, obtain mixture after, said mixture is carried out the constant temperature sintering.The prior art of comparing, the present invention uses microwave sintering or microwave sintering and resistance heating acting in conjunction to come mixture is carried out the constant temperature sintering.Microwave sintering can make each molecule in the mixture under the effect of the high-frequency electric field of microwave, shake frictional heat fast; Owing to be to act on simultaneously,, be heated evenly so each part of mixture can heat simultaneously; Make the positive electrode particle diameter that obtains behind the sintering even; Particle size distribution range is narrow, therefore can know its chemical property excellence by inference, and especially reversible capacity and cycle characteristics are improved.
According to the present invention, the microwave frequency of said microwave sintering is preferably 0.915～28GHz.Sintering time is preferably 10～96min, 10～30h time decreased of the resistance heating of comparing sintering, reduced energy consumption.The microwave sintering apparatus that the present invention uses is industrial microwave oven, preferably buys from ChangSha SYNO-THERM Co., Ltd., and model is HAMiLab-C1500,1600 ℃ of maximum operating temperatures, and the microwave output frequency is adjustable continuously.
According to the present invention, said microwave sintering preferably is controlled to be 3 stages, at first mixture is heated to 500～550 ℃ from room temperature, is warming up to 750～1000 ℃ then and continues heating, 500～800 ℃ of annealing down, obtains spinel-type nickel manganate cathode material for lithium at last.Heating process is divided into 3 stages can effectively controls the sintering process of mixture, make the positive electrode particle diameter that obtains behind the sintering more even, the integrity degree of lattice is better.
Embodiment 1:
With lithium hydroxide, nickel acetate, manganese acetate, lithium bromide, oxalic acid according to 1.01: 0.5: 1.5: 0.05: 3 mixed in molar ratio, carry out dry ball milling (rotating speed is 300rppm, ball milling time 5h, ratio of grinding media to material is 10: 1).The gained powder is placed 550 ℃ of following constant temperature sintering 0.2h of microwave air atmosphere stove, 900 ℃ of following constant temperature sintering 0.5h then, 600 ℃ of annealing 0.5h naturally cool to room temperature and obtain spinel-type transition metal oxide material LiNi again
0.5Mn
1.5O
3.95Br
0.05Can be known that by accompanying drawing 1 the spinel-type transition metal oxide material of gained bromine doping vario-property does not have dephasign, particle size distribution is even, and the material of present embodiment preparation is as shown in Figure 2.
Embodiment 2:
With lithium carbonate, nickel acetate, manganese acetate, lithium bromide, oxalic acid according to 0.505: 0.5: 1.5: 0.01: 2.5 mixed in molar ratio, carry out wet method method ball milling (rotating speed is 500rppm, ball milling time 10h, ratio of grinding media to material is 10: 1).Then the gained powder is placed 550 ℃ of following constant temperature sintering 2h of conventional resistance-type heating furnace, 850 ℃ of following constant temperature sintering 18h then, 500 ℃ of annealing 8h naturally cool to the spinel-type transition metal oxide material LiNi that room temperature obtains the bromine doping vario-property again
0.5Mn
1.5O
3.99Br
0.01With mass ratio is that 8: 1: 1 gained positive electrode, Kynoar, carbon black mixes in the N-methyl pyrrolidone and process cell size; The gained slurry is coated on the aluminium film back vacuumize 12h under 120 ℃ of conditions obtains the positive electrode for battery material, at last gained positive electrode and barrier film, electrolyte, lithium sheet negative pole, pad etc. are assembled into button cell.
Comparative example 1
With lithium carbonate, nickel acetate, manganese acetate, oxalic acid according to 0.505: 0.5: 1.5: 2.5 mixed in molar ratio, carry out wet ball grinding, rotating speed is 500rppm, ball milling time 10h, ratio of grinding media to material is 10: 1.Then the gained powder is placed 550 ℃ of following constant temperature sintering 2h of conventional resistance-type heating furnace, 850 ℃ of following constant temperature sintering 18h then, 500 ℃ of annealing 8h naturally cool to room temperature and obtain spinel-type transition metal oxide material LiNi again
0.5Mn
1.5O
4Method according to embodiment 2 prepares button cell.
Can be known that by accompanying drawing 3 battery discharge capacity under the 5C current density of embodiment 2 preparation positive electrode preparations can reach 108mAh/g, 50 circulation back capability retentions are greater than 90%; And battery discharge capacity under the 5C current density of the positive electrode preparation of comparative example 1 preparation is merely 100mAh/g, and 50 times circulation back capability retention is lower than 80%.
Embodiment 3:
With lithium carbonate, nickel oxide, manganese dioxide, lithium chloride according to 0.605: 0.2: 0.6: 0.2 mole proportioning is mixed, and adds the solution that deionized water is made into 0.2mol/L.Get gained solution 200ml and carry out freeze drying 12h; The gained powder is placed 550 ℃ of following constant temperature sintering 0.3h of microwave air atmosphere stove; 750 ℃ of following constant temperature sintering 1h then, 800 ℃ of annealing 0.5h naturally cool to room temperature and obtain Cl doping vario-property stratiform transition metal oxide Li again
1.2Ni
0.2Mn
0.6Cl
0.2O
1.8
Use the positive electrode of present embodiment preparation, use the method for embodiment 2 to prepare button cell, and said battery is carried out Electrochemical Detection, testing result shows that the positive electrode electrochemical reversible capacity of the present invention's preparation reaches 250mAh/g, and cycle performance is excellent.
Embodiment 4:
The lithium acetate, nickel acetate, manganese acetate, the lithium fluoride that concentration are respectively 1.2M, 0.2M, 0.6M, 0.08M join in the citric acid that concentration is 2M; To mixed solution and dripping ammoniacal liquor to solution PH=7, solution needs constant temperature to be 80 ℃ and to carry out magnetic agitation during dropping then.Gained solution obtains mixed powder with the dry spraying machine drying of high speed centrifugation, and feedstock solution speed is 10ml/min; The orifice gas flow is controlled by compressed-air actuated pressure, and pressure is controlled at 0.4MPa; Temperature of inlet air is 200 ℃, and outlet temperature is 80 ℃.The gained powder is placed 550 ℃ of following constant temperature sintering 0.3h of microwave air atmosphere stove, 800 ℃ of following constant temperature sintering 1h then, 600 ℃ of annealing 0.5h naturally cool to room temperature and obtain fluorine doping vario-property stratiform transition metal oxide material Li again
1.2Ni
0.2Mn
0.6F
0.08O
1.92
Use the positive electrode of present embodiment preparation, use the method for embodiment 2 to prepare button cell, and said battery is carried out Electrochemical Detection, testing result shows that the positive electrode electrochemical reversible capacity of the present invention's preparation reaches 280mAh/g, and cycle performance is excellent.
Embodiment 5:
The nickel acetate, lithium acetate, manganese acetate, the lithium bromide that concentration are respectively 0.1M, 0.2M, 0.3M, 0.08M join in the citric acid that concentration is 0.6M; To mixed solution and dripping ammoniacal liquor to solution PH=7, solution needs constant temperature to be 70 ℃ and to carry out magnetic agitation during dropping then.Then solution is heated to 80 ℃, magnetic agitation 24h, gained liquid are gel state by the collosol state transition gradually.The gained gel is obtained the powder precursor at air drying.The gained powder is placed 550 ℃ of following constant temperature sintering 0.1h of microwave air atmosphere stove, 1000 ℃ of following constant temperature sintering 0.5h then, 600 ℃ of annealing 0.5h naturally cool to room temperature and obtain bromine doping vario-property spinel-type transition metal oxide material again.
Use the positive electrode of present embodiment preparation, use the method for embodiment 2 to prepare button cell, and said battery is carried out Electrochemical Detection, testing result shows that the positive electrode electrochemical reversible capacity of the present invention's preparation reaches 145mAh/g, and cycle performance is excellent.
Embodiment 6:
The lithium acetate, nickel acetate, cobalt acetate, manganese acetate, the lithium bromide that concentration are respectively 0.1M, 0.2M, 0.13M, 0.13M, 0.54M, 0.03M join in the citric acid that concentration is 0.6M; To mixed solution and dripping ammoniacal liquor to solution PH=7, solution needs constant temperature to be 60 ℃ and to carry out magnetic agitation during dropping then.Gained solution is hydro-thermal reaction 18h under 180 ℃ of conditions of hydrothermal reaction kettle; To wash back gained powder then and place 550 ℃ of following constant temperature sintering 2.5h of conventional resistance-type heating furnace; 850 ℃ of following constant temperature sintering 20h then; 500 ℃ of annealing 10h naturally cool to room temperature and obtain bromine doping vario-property stratiform transition metal oxide material Li again
1.2Ni
0.13Co
0.13Mn
0.54Br
0.03O
1.97
Use the positive electrode of present embodiment preparation, use the method for embodiment 2 to prepare button cell, and said battery is carried out Electrochemical Detection, testing result shows that the positive electrode electrochemical reversible capacity of the present invention's preparation reaches 260mAh/g, and cycle performance is excellent.
Embodiment 7:
Through liquid phase coprecipitation prepared (Ni
1/4Mn
3/4) CO
3, precipitation reagent is a sodium carbonate, and complexing agent is an ammoniacal liquor, and PH is fixed as 7.5 in the course of reaction, and 60 ℃ of temperature are again with (Ni
1/4Mn
3/4) CO
3Place 500 ℃ of following constant temperature sintering 3h of resistance-type heated air atmosphere furnace to obtain (Ni
1/4Mn
3/4)
3O
4With lithium hydroxide, lithium bromide and Ni, Mn oxide is that 0.27: 0.1: 1 mass ratio mixes, and carries out mechanical lapping.The gained powder is placed 550 ℃ of following constant temperature sintering 0.1h of microwave air atmosphere stove, 900 ℃ of following constant temperature sintering 0.5h then, 600 ℃ of annealing 0.2h naturally cool to room temperature and obtain bromine doping vario-property spinel-type transition metal oxide material again.
Use the positive electrode of present embodiment preparation, use the method for embodiment 2 to prepare button cell, and said battery is carried out Electrochemical Detection, testing result shows that the positive electrode electrochemical reversible capacity of the present invention's preparation reaches 138mAh/g, and cycle performance is excellent.
Embodiment 8:
Lithium bromide mixed according to 0.1: 1 mole proportioning with spinel-type nickel LiMn2O4 carry out wet method method ball milling, rotating speed is 400rppm, ball milling time 8h, and ratio of grinding media to material is 10: 1.Then the gained powder is placed 550 ℃ of following constant temperature sintering 2h of conventional resistance-type heating furnace, 850 ℃ of following constant temperature sintering 18h then, 500 ℃ of annealing 8h naturally cool to the spinel-type transition metal oxide material that room temperature obtains the bromine doping vario-property again.
More than a kind of anode material for lithium-ion batteries provided by the invention and preparation method thereof has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and execution mode; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
Claims (10)
1. an anode material for lithium-ion batteries is characterized in that, comprises that general formula is Li
1+xMX
δO
ε-δCompound; Wherein M is one or more among Ni, Co, the Mn; X is one or more among F, Cl, Br, I and the S; 0＜x≤0.33,0＜δ≤0.2,0＜ε≤10.
2. positive electrode according to claim 1 is characterized in that, said M is Ni
αCo
βMn
γ, 0≤α≤1,0≤β≤1,0≤γ≤1, and α, β, γ are not zero simultaneously.
3. the preparation method of the described anode material for lithium-ion batteries of claim 1 is characterized in that, comprising:
A) Li source compound, the compound that contains M, the compound that contains X and additive are mixed, obtain mixture;
B) mixture that step a) is obtained is heat-treated, sintering, and obtaining general formula is Li
1+xMX
δO
ε-δAnode material for lithium-ion batteries; Wherein M is one or more among Ni, Co, the Mn; X is one or more among F, Cl, Br, I and the S; 0＜x≤0.33,0＜δ≤0.2,0＜ε≤10.
4. preparation method according to claim 3 is characterized in that, said Li source compound is one or more in hydroxide, oxide, sulfate, carbonate, nitrate and the acetate of lithium.
5. preparation method according to claim 3; It is characterized in that; The compound of the said M of containing is hydroxide, oxide, sulfate, carbonate, the nitrate of nickel; The hydroxide of manganese, oxide or sulfate, carbonate, nitrate, one or more in the hydroxide of cobalt, oxide or sulfate, carbonate, the nitrate.
6. preparation method according to claim 3 is characterized in that, the compound of the said X of crying out is the compound that contains F, Cl, Br, I and S.
7. preparation method according to claim 3 is characterized in that, said additive is one or more in oxalic acid, ammoniacal liquor, sodium carbonate, potash, NaOH, potassium hydroxide, neopelex, the citric acid.
8. preparation method according to claim 7 is characterized in that said additive amount accounts for the 10wt%～50wt% of mixture gross mass.
9. preparation method according to claim 3 is characterized in that step a) is specially:
A1) a1) that Li source compound, the compound that contains M, the compound that contains X and additive is soluble in water, obtain mixed solution;
A2) said mixed solution is dry, obtain mixture.
10. preparation method according to claim 3 is characterized in that step b is specially:
B1) mixture that step a) is obtained is being heated to 500～550 ℃ from room temperature;
B2) with step b1) mixture that obtains is heated to 750～1000 ℃;
B3) with step b2) mixture that obtains is 500～800 ℃ of annealing down, obtains anode material for lithium-ion batteries.
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| CN114620775B (en) * | 2022-03-15 | 2023-03-24 | 北京理工大学 | Double-anion co-doped lithium-rich manganese-based composite material, preparation method and application |
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