CN104485452A - High-temperature type lithium manganate anode material for power lithium ion battery and preparation method of high-temperature type lithium manganate anode material - Google Patents

High-temperature type lithium manganate anode material for power lithium ion battery and preparation method of high-temperature type lithium manganate anode material Download PDF

Info

Publication number
CN104485452A
CN104485452A CN201410843002.7A CN201410843002A CN104485452A CN 104485452 A CN104485452 A CN 104485452A CN 201410843002 A CN201410843002 A CN 201410843002A CN 104485452 A CN104485452 A CN 104485452A
Authority
CN
China
Prior art keywords
core
positive electrode
mole
metallic element
lithium
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
CN201410843002.7A
Other languages
Chinese (zh)
Other versions
CN104485452B (en
Inventor
郝振佳
江卫军
李化一
张溪
苏迎春
崔妍
文博
白珍辉
朱晓沛
庞自钊
高利亭
吴剑文
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.)
Beijing mengguli New Material Technology Co.,Ltd.
Original Assignee
Zhongxinguoan Mengguli Power Supply 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 Zhongxinguoan Mengguli Power Supply Technology Co Ltd filed Critical Zhongxinguoan Mengguli Power Supply Technology Co Ltd
Priority to CN201410843002.7A priority Critical patent/CN104485452B/en
Publication of CN104485452A publication Critical patent/CN104485452A/en
Application granted granted Critical
Publication of CN104485452B publication Critical patent/CN104485452B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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 a high-temperature type lithium manganate anode material for a power lithium ion battery. The high-temperature type lithium manganate anode material consists of a core material as shown in a formula Li1+xMn2-y-zAyQzO4, and a coating layer on the surface of the core material, wherein the coating layer is one or more of cobaltosic oxide, aluminum oxide and nickel protoxide. The anode material is excellent in high-temperature property, and is good in specific discharge capacity, capacity retention ratio and electrochemical circulation property at high temperature. In addition, the preparation method of the anode material disclosed by the invention is simple in production process, easy to achieve and low in cost, and can be applied to large-scale industrialization production.

Description

A kind of power lithium-ion battery high-temperature manganic acid lithium cathode material and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery, particularly a kind of power lithium-ion battery high-temperature manganic acid lithium cathode material and preparation method thereof.
Background technology
In today that environmental problem and energy crisis are increasingly sharpened, be that the New Energy Industry of representative is in the ascendant with electric automobile.Wherein, the advantages such as operating voltage is high, energy density is large owing to having, lightweight, volume is little, fail safe is good, cycle life is good for lithium ion battery, environmental protection, have development prospect widely in electric automobile power battery field.
The anode material for lithium-ion batteries of large-scale application mainly contains cobalt acid lithium, spinel lithium manganate, ternary material and LiFePO4 etc. in the market.Compared with other positive electrodes, LiMn2O4, due to features such as cost are low, synthesis technique is simple, security performance is excellent, has application prospect widely in power lithium-ion battery market.But owing to there is the normal temperature particularly shortcoming and defect such as fast, the high-temperature storage performance difference of capacity attenuation under high temperature (55 DEG C), seriously constrain its application in high-end fields such as power lithium-ion batteries.Therefore emphasis is needed to improve the high temperature cyclic performance of LiMn2O4, with the application requirement making it meet power lithium-ion battery.
Summary of the invention
In order to solve the problem, present inventor has performed and study with keen determination, found that: first by the precursor of compound body doped with metal element A, then after this precursor being mixed with the oxide containing metallic element, lithium source, high-temperature roasting obtains body phase and the core showing to adulterate mutually, and described core carries out Surface coating, after heat-treating with the additive containing metallic element, obtain power lithium-ion battery high-temperature manganic acid lithium cathode material, thus complete the present invention.
The object of the present invention is to provide a kind of power lithium-ion battery high-temperature manganic acid lithium cathode material, this positive electrode comprises with lower part:
Core and
Coating layer,
Wherein, described core is by shown in formula I:
Li 1+xMn 2-y-zA yQ zO 4
Formula I
In described formula I, metal element A be selected from Al, Mg, Co one or more, metallic element Q be selected from Al, Mg, Co, Nb, Cr one or more,
In described formula I, 0≤x≤0.2,0<y≤0.18,0<z≤0.1, and 0<y+z≤0.2,1≤y/z≤10,
Described coating layer is at described core surfaces, described coating layer is one or more in cobaltosic oxide, alundum (Al2O3), nickel protoxide, and in coating layer, the mole sum of metallic element is metallic element with the ratio of the mole in core: oxygen=0.003 ~ 0.15:1.
Another object of the present invention is to the preparation method providing power lithium-ion battery high-temperature manganic acid lithium cathode material, the method comprises the following steps:
The preparation of the presoma of step one, positive electrode:
1) soluble-salt of manganese being mixed with mixed aqueous solution with the soluble-salt containing elements A joins in reactor, the total mol concentration of mixed aqueous solution is 1 ~ 3mol/l, soluble-salt and the rate of charge of the soluble-salt containing metal element A of manganese are make the manganese element in the soluble-salt of manganese and are Mn:A=(2-y-z): y containing the mol ratio of metal element A in the soluble-salt of metal element A, 0<y≤0.18,0<z≤0.1, and, 0<y+z≤0.2,1≤y/z≤10
Wherein, the soluble-salt of manganese be selected from manganese sulfate, manganese nitrate one or more, the soluble-salt containing metal element A be selected from sulfate containing metal element A, nitrate, hydrochloride one or more, described metal element A is Al, Mg and Co,
2) under agitation, to step 1) described in reactor in respectively add sodium hydrate aqueous solution and ammonia spirit simultaneously, react 6 ~ 20 hours, simultaneously, the pH of the hierarchy of control is 8 ~ 10, the reaction temperature of system is 40 ~ 60 DEG C, now constantly precipitates the coprecipitate that output contains the hydroxide of manganese element and metal A element
Wherein, the concentration of sodium hydrate aqueous solution is 1 ~ 5mol/l, and the concentration of ammonia spirit is 1 ~ 5mol/l,
3) by step 2) in the coprecipitate that obtains dry at 100 ~ 120 DEG C, obtain the bulk phase-doped spherical mangano-manganic oxide having metal element A, i.e. the presoma of positive electrode;
Step 2, preparation by the core shown in formula I:
1) by gained presoma in step one, mix with lithium source and the oxide containing metallic element Q, grind, mix, its rate of charge is the mole of the element A made in presoma, the ratio of the mole of Q element in Li element mole in lithium source, oxide containing metallic element Q is A:Li:Q=y:(1+x): z, 0≤x≤0.2,0<y≤0.18,0<z≤0.1, and, 0<y+z≤0.2,1≤y/z≤10
Wherein, lithium source is one or more in lithium carbonate, lithium hydroxide and lithium nitrate, and the oxide containing metallic element Q is containing one or more in the oxide of Al, Mg, Co, Nb, Cr,
2) by step 1) in the roasting 5 ~ 30 hours at 600 ~ 900 DEG C of the mixture that mixes, be then cooled to 500 DEG C with the speeds control of 1 ~ 2 DEG C/min and continue roastings, after roasting completes, cooling, pulverizes, and screening, obtains by the core shown in formula I,
The preparation of step 3, positive electrode:
1) mix by the core shown in formula I with the additive M containing metallic element, grind, mix, rate of charge is make the mole of additive M containing metallic element be 0.003 ~ 0.15:1 with the ratio of the mole of core,
Wherein, the additive M containing metallic element is one or more in cobalt carbonate, cobalt hydroxide, aluminium powder, nickel protoxide, and the meso-position radius of described additive is less than 3 microns,
2) by step 1) in mixture heat treatment 2 ~ 15h at the temperature of 400 ~ 800 DEG C of mixing, cooling, after screening, obtains positive electrode, i.e. power lithium-ion battery high-temperature manganic acid lithium cathode material.
Another object of the present invention is the power lithium-ion battery high-temperature manganic acid lithium cathode material that the provides purposes for power lithium-ion battery positive electrode.
Power lithium-ion battery high-temperature manganic acid lithium cathode material provided by the invention has excellent resistance to elevated temperatures, and at high temperature, has good specific discharge capacity, capability retention and electrochemistry cycle performance.
In addition, the production technology adopted in the preparation method of positive electrode provided by the invention is simple, be easy to realize, and cost is low, can be applied in industrial production on a large scale.
Accompanying drawing explanation
Fig. 1 a is the XRD spectra of gained presoma in embodiment 1;
Fig. 1 b is the XRD spectra of gained core in embodiment 1;
Fig. 1 c is the XRD spectra of gained final products in embodiment 1;
Fig. 2 a is the scanning electron microscope (SEM) photograph of gained presoma in embodiment 1;
Fig. 2 b is the scanning electron microscope (SEM) photograph of gained core in embodiment 1;
Fig. 2 c is the scanning electron microscope (SEM) photograph of gained final products in embodiment 1;
Fig. 3 a is the grain size distribution of gained presoma in embodiment 1;
Fig. 3 b is the grain size distribution of gained core in embodiment 1;
Fig. 3 c is the grain size distribution of gained final products in embodiment 1;
Fig. 4 a is the dispersion spectrogram of gained presoma in embodiment 1;
Fig. 4 b is the dispersion spectrogram of gained core in embodiment 1;
Fig. 4 c is the dispersion spectrogram of gained final products in embodiment 1;
Fig. 5 is the first charge-discharge curve comparison figure of positive electrode in gained final products and comparative example 1 in embodiment 1;
Fig. 6 is the full cycle performance of battery comparison diagram of positive electrode in gained final products and comparative example 1 in embodiment 1.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will illustrate along with these and become more clear, clear and definite.
According to an aspect of the present invention, provide a kind of power lithium-ion battery high-temperature manganic acid lithium cathode material, this positive electrode comprises with lower part:
Core and
Coating layer,
Wherein, described core is by shown in formula I:
Li 1+xMn 2-y-zA yQ zO 4
Formula I
Described coating layer is at described core surfaces, and coating layer is one or more in cobaltosic oxide, alundum (Al2O3), nickel protoxide.
In above-mentioned formula I, metal element A be selected from Al, Mg, Co one or more, metallic element Q be selected from Al, Mg, Co, Nb, Cr one or more, the combination of preferred Al, Cr or Mg and Nb.
By above-mentioned positive electrode after inductively coupled plasma atom diverging light spectrometry (ICP) and dispersion spectrum (EDS) detect, draw 0≤x≤0.2, especially, preferably 0.1≤x≤0.2.
After ICP and EDS detects, learn in above-mentioned formula I, 0<y≤0.18,0<z≤0.1, and 0<y+z≤0.2,1≤y/z≤10, especially, preferably 0.05≤y+z≤0.15, or/and 1≤y/z≤3.
After ICP and EDS detects, learn in above-mentioned positive electrode, in described coating layer, the mole sum of metallic element is metallic element with the ratio of the mole in the core shown in formula I: core=0.003 ~ 0.15:1, preferably 0.015 ~ 0.09:1.
When coating layer is cobaltosic oxide, the mole of the cobalt element in coating layer is Co with the ratio of the mole of core: core=0.003 ~ 0.15:1, preferably 0.015 ~ 0.09:1.
When coating layer is alundum (Al2O3), the mole of the cobalt element in coating layer is Al with the ratio of the mole of core: core=0.002 ~ 0.1:1, preferably 0.01 ~ 0.06:1.
When coating layer is nickel protoxide, the mole of the nickel element in coating layer is Ni with the ratio of the mole of core: core=0.001 ~ 0.05:1, preferably 0.005 ~ 0.03:1.
The spinel structure of power lithium-ion battery high-temperature manganic acid lithium cathode material provided by the invention to be a kind of space group be Fd3m, by this positive electrode after X-ray diffraction test, its result as illustrated in figure 1 c, known according to X-ray diffraction test, its XRD collection of illustrative plates and standard diagram coincide, and can learn thus by positive electrode provided by the invention, and its crystal formation is excellent, lattice is perfect, basic zero defect.
Above-mentioned positive electrode is the homogeneous and spherical solid particles of structure consolidation of form, when the cumulative particle size distribution percentage by volume of solid particle reaches 50%, particle diameter corresponding to it is tested, the meso-position radius (D50) obtaining solid particle is thus 5 ~ 20 microns, and even particle size distribution.Especially, preferred meso-position radius is 8 ~ 12 microns.
Above-mentioned positive electrode can arrive higher tap density, is 1.8 ~ 2.5g/cm 3.
Using above-mentioned positive electrode as positive pole, using metal lithium sheet as negative pole, be assembled into 18605 type button cells, test at the temperature of 55 DEG C, learn that the specific discharge capacity of this positive electrode is 90 ~ 120mAh/g, after 50 circulations, capability retention is more than 97%.
Using above-mentioned positive electrode as positive pole, the capacity of being assembled into is the 055570 type flexible-packed battery of 1Ah, then at 55 DEG C, carries out loop test, learns that the cycle life of full battery 80% is 400 ~ 600 times.
Power lithium-ion battery high-temperature manganic acid lithium cathode material provided by the present invention, by bulk phase-doped acquisition presoma, makes the corresponding ion of metal element A occupy Mn3+ position in LiMn2O4 lattice, thus decreases Mn in LiMn2O4 3+content, to reduce Mn 3+john-Teller distortion and the capacity attenuation that causes, in addition, the ion of the corresponding divalent state of metal element A also can by Mn 3+be oxidized to Mn 4+, thus further decrease Mn in LiMn2O4 lattice 3+content, therefore, significantly improves LiMn2O4 as the fast problem of capacity attenuation during positive electrode.
According to the present invention, presoma is adulterated mutually by table again and obtains the core shown in formula I, make metallic element Q improve Mn in the top layer of positive electrode second particle 3+content, therefore, under the prerequisite as far as possible ensureing anode material discharging capacity, improve its cycle performance to greatest extent.
In addition, the present invention is also by the core surfaces coated metal oxide shown in formula I, decrease the contact of core and electrolyte, thus the dissolving in the electrolytic solution of effective alleviation manganese ion, the resistance to elevated temperatures of positive electrode is significantly improved, thus makes positive electrode provided by the invention meet the application requirement in electrokinetic cell.
According to a further aspect in the invention, provide a kind of preparation method preparing power lithium-ion battery high-temperature manganic acid lithium cathode material, the method comprises the following steps:
The preparation of the presoma of step one, positive electrode,
Step 2, preparation by the core shown in formula I,
The preparation of step 3, positive electrode.
In above-mentioned steps one, the preparation method of the presoma of described high-temperature manganic acid lithium cathode material does not limit especially, the methods such as high-temperature solid phase reaction method, sol-gal process and coprecipitation.
In preferred implementation method, the preparation method of the presoma of positive electrode comprises the following steps:
1) soluble-salt of manganese being mixed with mixed aqueous solution with the soluble-salt containing elements A joins in reactor, the total mol concentration of mixed aqueous solution is 1 ~ 3mol/l, soluble-salt and the rate of charge of the soluble-salt containing metal element A of manganese are make the manganese element in the soluble-salt of manganese and are Mn:A=(2-y-z): y containing the mol ratio of metal element A in the soluble-salt of metal element A, namely rate of charge is the metering ratio of the respective element in formula I, wherein, 0<y≤0.18, 0<z≤0.1, and 0<y+z≤0.2, 1≤y/z≤10.
Especially, 0.05≤y+z≤0.15, or/and 1≤y/z≤3.
In described step 1) in, the soluble-salt of manganese be selected from manganese sulfate, manganese nitrate one or more, soluble-salt containing metal element A be selected from sulfate containing metal element A, nitrate, hydrochloride one or more, described metal element A is Al, Mg and Co.
Especially, the sulfate preferably containing metal element A is or/and nitrate.
In described step 1) in, the soluble-salt of manganese and the soluble-salt containing metal element A are added in deionized water, form the mixed aqueous solution of manganese salt and the soluble-salt containing metal element A, in mixed aqueous solution, the summation of mole of manganese salt mole and the soluble-salt containing metal element A and the ratio of mixed aqueous solution volume are the total mol concentration of mixed aqueous solution.
In described step 1) in, mixed aqueous solution joins in reactor with certain speed, and wherein, adding speed is 0.5 ~ 3ml/min, especially, and preferred 1ml/min.
2) under agitation, to step 1) described in reactor in respectively add sodium hydrate aqueous solution and ammonia spirit simultaneously, react 6 ~ 20 hours, simultaneously, the pH of the hierarchy of control is 9 ~ 11, the reaction temperature of the hierarchy of control is 40 ~ 60 DEG C, now constantly precipitates the coprecipitate that output contains the hydroxide of manganese element and metal A element.
In described step 2) in, NaOH provides hydroxide ion as precipitation reagent, and ammoniacal liquor is as buffer, then contribute to coprecipitate and form spherical hydroxide.
In described step 2) in, the concentration of sodium hydrate aqueous solution is 1 ~ 5mol/l, and the concentration of ammonia spirit is 1 ~ 5mol/l.
In described step 2) in, the adding rate of ammonia spirit is 0.3 ~ 1ml/min, and especially, adding rate is 0.5ml/min.The adding rate of sodium hydrate aqueous solution makes the pH value of system remain between 9 to 11, then contribute to the coprecipitate output of hydroxide.
If the pH value of system is too low, be unfavorable for the growth of coprecipitate, cause the particle diameter of coprecipitate little, if the pH value of system is too high, then make coprecipitate easily decompose, be also unfavorable for the growth of coprecipitate.
In described step 2) in, the reaction temperature of system is 40 ~ 60 DEG C, if the temperature of system is too low, the particle diameter of coprecipitate then can be caused too small and closely knit second particle of reuniting cannot be formed, if temperature is too high, the rate of volatilization of ammoniacal liquor can be caused on the one hand fast, affect the growth of product, on the other hand, the precipitation of manganous hydroxide can be unstable at relatively high temperatures and decompose.
Especially, the reaction temperature of the hierarchy of control is 50 ~ 60 DEG C.
In described step 2) in, after reaction terminates, ageing can be continued 4 ~ 10 hours, especially, preferably 5 ~ 8 hours, further, preferably 5 hours.
In above-mentioned steps 2) in, stir speed (S.S.) does not limit especially, as long as system can be stirred, especially, and preferably 1100 ~ 1500r/min, further, preferred 1200r/min.
3) by step 2) in the coprecipitate that obtains dry at 100 ~ 120 DEG C, obtain the bulk phase-doped spherical mangano-manganic oxide having metal element A, i.e. the presoma of positive electrode.
The presoma meso-position radius (D50) prepared is 5 ~ 15 microns, is preferably 8 ~ 10 microns, and even particle size distribution.
In the preparation of the core of described step 2, carbon source and not being restricted containing the oxide of Q element and the hybrid mode of presoma, dry mixed, wet-mixed.
In a preferred embodiment, obtained by following preparation method such as formula the core shown in I:
1) by gained presoma in step one, mix with lithium source and the oxide containing metallic element Q, grind, mix, its rate of charge is the mole of the element A made in presoma, Li element mole in lithium source, the ratio of the mole of the Q element in the oxide containing metal Q element is A:Li:Q=y:(1+x): z, 0≤x≤0.2, preferably 0.1≤x≤0.2, 0<y≤0.18, 0<z≤0.1, and, 0<y+z≤0.2, 1≤y/z≤10, preferably 0.05≤y+z≤0.15, or/and preferred 1≤y/z≤3,
Wherein, lithium source is one or more in lithium carbonate, lithium hydroxide and lithium nitrate.
Wherein, the oxide containing metallic element Q is containing one or more in the oxide of Al, Mg, Co, Nb, Cr.
Especially, the oxide containing metallic element Q is the combination of aluminium oxide, magnesium oxide or magnesium oxide and niobium pentaoxide.
In a preferred embodiment, the oxide containing metallic element Q is nano-oxide.
In described step 1) in, the mode ground can be multiple, is not subject to concrete restriction, can select according to the actual requirements.In the present invention, especially, select ball milling in ball mill, make the mixing that lithium source, presoma and the oxide containing metallic element Q are full and uniform.
2) by step 1) in the roasting 5 ~ 30 hours at 600 ~ 900 DEG C of the mixture that mixes, be then cooled to 500 DEG C with the speeds control of 1 ~ 2 DEG C/min and continue roastings, after roasting completes, cooling, pulverizes, and screening, obtains by the core shown in formula I.
In above-mentioned steps 2) in, by step 1) in presoma, lithium source and after mixing containing the oxide of metallic element Q, roasting at 600 ~ 900 DEG C, in the process of roasting, can cause to have generated and be decomposed by the core generating portion shown in formula I, namely generate oxygen-containing defected core.
But the present inventor finds through research, and this decomposition is reversible.Mixture after roasting, will be lowered the temperature with the speeds control of 1 ~ 2 DEG C/min, and made temperature be down to 500 DEG C at 600 ~ 900 DEG C, then roasting is continued, in the process continuing roasting, due to the effect of oxygen composition in air, oxygen-containing defected core is obtained such as formula the core shown in I, i.e. Li 1+xmn 2-y-za yq zo 4.
In described step 2) in, cooling rate is not easily too fast, otherwise effect is bad.
Through detecting, learn that the meso-position radius (D50) of the core prepared is 5 ~ 20 microns, preferably 8 ~ 12 microns, and even particle size distribution.
In the preparation of the final products of described step 3, the adding method adding the additive of containing metal element in described core is not restricted, dry method or wet method.
Study discovery through the present inventor, the addition manner of the additive containing metallic element can be selected according to actual conditions and actual demand.
When the selected additive M good dispersion in a solvent containing metallic element, flow processability is good, then select wet method to add.
In addition, dry method is easy to operate, and cost, comparatively speaking, wet method cost is high, and not easy to operate.
In the process, final products, namely the preparation method of positive electrode comprises the following steps:
1) mix by the core shown in formula I with the additive M containing metallic element, grind, mix, rate of charge is make the mole of additive M containing metallic element be 0.001 ~ 0.05:4 with the ratio of the mole of core, especially, preferred 0.005 ~ 0.03:4.
Wherein, additive M containing metallic element is one or more in cobalt carbonate, cobalt hydroxide, aluminium powder, nickel protoxide, the meso-position radius (D50) of described additive is less than 3 microns, especially, one or more in preferred nano-calcium carbonate cobalt, nanoflakes and cobalt hydroxide, nanometer aluminium powder, nano oxidized sub-nickel.
In described step 1) in, the mode ground can be multiple, is not subject to concrete restriction, can select according to the actual requirements.In the present invention, especially, select ball milling in ball mill, make core and the additive M Homogeneous phase mixing containing metallic element.
2) by step 1) in mixed uniformly mixture heat treatment 2 ~ 15h at the temperature of 400 ~ 800 DEG C, cooling, after screening, obtain positive electrode.
After above-mentioned heat treatment step, the additive M containing metallic element is generating metal oxide by the core surfaces shown in formula I accordingly, thus forms coating layer.
Described metal oxide is one or more in cobaltosic oxide, alundum (Al2O3), nickel protoxide.
In described step 2) in, if heat treated temperature is greater than 500 DEG C, then after the heat treatment, system is cooled to 500 DEG C with the rate of temperature fall of 1 ~ 2 DEG C/min by system, then continues heat treatment.After heat treatment completes, obtain final products, it is by the core shown in formula I and form at the coating layer of core surfaces, is power lithium-ion battery high-temperature manganic acid lithium cathode material.
The production technology adopted in the preparation method of positive electrode provided by the invention is simple, is easy to realize, and cost is low, can be applied in industrial production on a large scale.
In accordance with a further aspect of the present invention, the power lithium-ion battery high-temperature manganic acid lithium cathode material provided is for the purposes of power lithium-ion battery positive electrode.
Positive electrode provided by the invention, by bulk phase-doped metallic element, decreases Mn in positive electrode 3+content, thus improve due to Mn 3+john-Teller to distort the problem of the capacity attenuation caused; Again by table phase doped metallic elements, further reduce Mn in positive electrode second particle top layer 3+content, under the prerequisite as far as possible ensureing anode material discharging capacity, improve its cycle performance to greatest extent; Finally by the stable metal oxide of Surface coating, decrease the contact of core and electrolyte, make the resistance to elevated temperatures of positive electrode obtain obvious improvement, therefore meet the application requirement of power lithium-ion battery.
embodiment
The present invention is further described below by way of instantiation.But these examples are only exemplary, do not form any restriction to protection scope of the present invention.
Embodiment 1
preparing core is: Li 1.08 mn 1.9 al 0.06+0.04 o 4 , coating layer is: 0.01Al 2 o 3 positive electrode
The preparation of step one, presoma:
1) 984g MnSO is taken respectively 4h 2o, 120g Al 2(SO 4) 318H 2o adds in deionized water, is mixed with mixed aqueous solution 2L, joins in CSTR reactor with the speed of 1ml/min,
2) prepare the sodium hydrate aqueous solution of 4mol/l and the ammonia spirit of 3mol/l, ammonia spirit and sodium hydrate aqueous solution peristaltic pump joined and fills it up with in the CSTR reactor of deionized water,
Wherein, the speed that adds controlling ammonia spirit is 0.5ml/min, and the pH value adding the system that speed makes controlling sodium hydrate aqueous solution is stabilized in 9.0 ± 0.5, controlling reaction temperature is 60 ± 2 DEG C, mixing speed 1200r/min, successive reaction 20h, then then ageing 5h
3) by step 2) in gained precipitate with deionized water washing, filter after, dry 5h in the air dry oven of 110 ± 5 DEG C, obtains the spherical mangano-manganic oxide precursor doped with Al element.
The preparation of step 2, core:
1) by gained precursor, lithium carbonate and nano aluminium oxide in step one according to the mol ratio of the Li element in Al element, lithium carbonate in presoma and the aluminium element in nano aluminium oxide be the ratio mixing of Al:Li:Al=0.06:1.08:0.04, ball milling, mix
2) at the roasting temperature 8h of 900 DEG C, then cool to 500 DEG C with the speeds control of 1.5 DEG C/min, proceed roasting, then cool, pulverize, screening, obtain core Li 1.08mn 1.9al 0.06+0.04o 4.
The preparation of step 3, final products:
1) by the core of gained in step 2 and nanometer aluminium powder with the ratio of the mole of core and the mole of aluminium powder for 1:0.02 rate of charge mixes, ball milling 2h, mixes,
2) by step 1) in homogeneous mixture after heat treatment 4h, with the rate of temperature fall of 1.5 DEG C/min, system is cooled to 500 DEG C, proceeds heat treatment at 800 DEG C, obtain final products, i.e. power ion battery high-temperature manganic acid lithium cathode material.
Record through Beckman particle size analyzer: the D50 of the granularity of gained presoma is 9.15 μm, the D50 of the granularity of gained core is 11.32 μm, and the D50 of the granularity of end product is 11.08 μm.
End product is after ICP and EDS detects, and to be core be products therefrom: Li 1.08mn 1.9al 0.06+0.04o 4, coating layer is: 0.01Al 2o 3, tap density is 2.23g/cm 3.
Embodiment 2
preparing core is: Li 1.102 mn 1.9 co 0.05 cr 0.05 o 4 , coating layer is: the positive electrode of 0.005NiO
The preparation of step one, presoma:
1) Mn (NO that 2097g mass percent is 50% is taken respectively 3) 2the aqueous solution, 59g Co (NO 3) 26H 2o adds in deionized water, is mixed with mixed aqueous solution 2L, joins in CSTR reactor with the speed of 1ml/min,
2) prepare the aqueous sodium carbonate of 2mol/L and the ammonia spirit of 3mol/L, ammonia spirit and aqueous sodium carbonate peristaltic pump joined and fills it up with in the CSTR reactor of deionized water,
Wherein, controlling the speed that adds of ammonia spirit is 0.5ml/min, and the speed that adds controlling aqueous sodium carbonate makes pH value be stabilized in 7.0 ± 0.05, and controlling reaction temperature is 60 ± 2 DEG C, mixing speed 1200r/min, successive reaction 20h, then then ageing 5h,
3) by step 2) in gained precipitate with deionized water washing, filter, at 120 DEG C, after drying, at the roasting temperature 8h of 500 DEG C, obtain the many spaces spherical alumina manganese precursor doped with Co element.
The preparation of step 2, core:
1) by gained precursor, lithium carbonate and chromium oxide in step one according to the mol ratio of the Li element in Co element, lithium carbonate in presoma and the chromium element in chromium oxide be the ratio mixing of Co:Li:Cr=0.05:1.102:0.05, ball milling, mix
2) at the roasting temperature 10h of 850 DEG C, then cool to 500 DEG C with the speeds control of 1.5 DEG C/min, proceed roasting, cooling, pulverize, screening, obtain core Li 1.102mn 1.9co 0.05cr 0.05o 4.
The preparation of step 3, final products
1) by the core of gained in step 2 and nano oxidized sub-nickel with the ratio of the mole of core and the mole of nickel element in nickel oxide for core: the rate of charge of nickel protoxide=4:0.005 mixes, and ball milling 2h, mixes,
2) by step 1) in homogeneous mixture after heat treatment 6h, with the rate of temperature fall of 1.5 DEG C/min, system is cooled to 500 DEG C, proceeds heat treatment at 750 DEG C, obtain final products, i.e. power ion battery high-temperature manganic acid lithium cathode material.
Record through Beckman particle size analyzer: the D50 of the granularity of gained presoma is 8.54 μm, the D50 of the granularity of gained core is 10.78 μm, and the D50 of the granularity of end product is 10.50 μm.
End product is after ICP and EDS detects, and to be core be products therefrom: Li 1.102mn 1.9co 0.05cr 0.05o 4, coating layer is: 0.005NiO, and tap density is 2.17g/cm 3.
Embodiment 3
preparing core is:
Li 1.14 Mn 1.86 (Mg 0.05 Co 0.05 )(Mg 0.035 Nb 0.05 )O 4
coating layer is: 0.03Co 3 o 4 positive electrode
The preparation of step one, presoma:
1) take spherical manganese dioxide 500g, nano-cobaltic-cobaltous oxide 3.53g, nano magnesia 1.77g respectively, after ball milling 2h, mix,
2) by step 1) in homogeneous mixture at 1000 DEG C, be incubated 10h after, pulverize, sieve, obtain the required spherical mangano-manganic oxide precursor doped with Mg element and Co element.
The preparation of step 2, core:
1) be the rate of charge mixing of Mg:Li:Mg:Nb=0.05:1.14:0.035:0.05 by gained precursor, lithium nitrate and nano magnesia in step one, niobium pentaoxide according to the mol ratio of the Li element in Mg element, lithium nitrate in presoma and the Mg element in magnesium oxide, the Nb element in niobium pentaoxide, after ball milling 2h, mix
Wherein, add absolute methanol as dispersant in mixed process, the rate of charge of mixture and absolute methanol is that every 100g mixture need add 30ml absolute methanol.
2) at the roasting temperature 20h of 750 DEG C, then cool to 500 DEG C with the speeds control of 1.5 DEG C/min, proceed roasting, then cool, pulverize, screening, obtain core Li 1.14mn 1.86(Mg 0.05co 0.05) (Mg 0.035nb 0.05) O 4.
The preparation of step 3, final products:
1) by the core of gained in step 2 and nanoflakes and cobalt hydroxide with the ratio of the mole of core and the mole of cobalt element in cobalt hydroxide for 4:0.09 rate of charge mixes, add absolute methanol again as dispersant, every 100g mixture needs the dispersant of 10ml, ball milling 1h, mix
2) then heat treatment 10h at 500 DEG C, obtains final products, i.e. power ion battery high-temperature manganic acid lithium cathode material.
Record through Beckman particle size analyzer: the D50 of the granularity of gained presoma is 9.83 μm, the D50 of the granularity of gained core is 11.59 μm, and the D50 of the granularity of end product is 11.28 μm.
End product is after ICP and EDS detects, and to be core be products therefrom: Li 1.14mn 1.86(Mg 0.05co 0.05) (Mg 0.035nb 0.05) O 4, coating layer is: 0.03Co 3o 4, tap density is 2.37g/cm 3.
Comparative example 1
1) take LITHIUM BATTERY electrolytic manganese dioxide 500g respectively, battery-level lithium carbonate 109.33g, nano aluminium oxide 54.66g, after ball milling 2h, mix,
2) by step 1) in homogeneous mixture at the roasting temperature 20h of 840 DEG C, then cool to 500 DEG C with the speeds control of 1.5 DEG C/min, proceed roasting, then cool, pulverize, screening, obtain comparative example.
Record through Beckman particle size analyzer: the D50 of the granularity of comparative example is 8.13 μm.End product is after ICP and EDS detects, and products therefrom is: Li 1.09mn 1.9al 0.01o 4, tap density is 1.73g/cm 3.
test example
x-ray diffraction analysis
X-ray diffraction analysis is carried out to the presoma of embodiment 1 gained, core and final products, obtains XRD spectra, respectively as shown in Fig. 1 a, Fig. 1 b, Fig. 1 c.
Analyzed can be learnt by Fig. 1 a, Fig. 1 b, Fig. 1 c, the presoma that the present invention obtains, core and final products, all have crystal structure, simultaneously by sharp-pointed diffraction maximum, can learn that the crystallinity of the positive electrode of acquisition is good.
scanning electron microscope analysis (SEM)
Scanning electron microscope analysis is carried out to the presoma of embodiment 1 gained, core and final products, obtains SEM photo, respectively as shown in Fig. 2 a, Fig. 2 b, Fig. 2 c.
Analyzed can be learnt by Fig. 2 a, Fig. 2 b, Fig. 2 c, it is homogeneous that the presoma that the present invention obtains, core and final products are form, the spheric granules of structure consolidation, and there is the spheric granules of coating layer on the surface of final products., can also learn, being evenly distributed of the presoma obtained, core and final products is concentrated meanwhile, soilless sticking phenomenon.
domain size distribution is tested
By Beckman laser particle analyzer, domain size distribution test is carried out to the presoma of embodiment 1 gained, core and final products, obtains grain size distribution, respectively as shown in Fig. 3 a, Fig. 3 b, Fig. 3 c.
Analyzed can be learnt by Fig. 3 a, Fig. 3 b, Fig. 3 c, the particle size distribution of the presoma that the present invention obtains, core and final products all in normal distribution, and is evenly distributed.
electrochemistry is tested
One, using gained positive electrode in embodiment 1 ~ 3 and comparative example 1 as positive pole, using metal lithium sheet as negative pole, be assembled into 2032 type button cells respectively, then electric discharge specific capacity and 50 capability retentions at 55 DEG C, result is as shown in table 1:
Table 1
In addition, by the first charge-discharge curve comparison figure of positive electrode in gained final products in embodiment 1 and comparative example 1, as shown in Figure 5, can learn:
The battery be made up of embodiment 1 gained positive electrode, capacity with corresponding respectively after electric discharge after charging is substantially identical, and the battery be made up of the positive electrode of comparative example gained, differ greatly with capacity corresponding respectively after electric discharge after charging, then illustrate that positive electrode resistance to elevated temperatures provided by the invention is good, and there is higher specific discharge capacity.
Two, using gained positive electrode in embodiment 1 ~ 3 and comparative example 1 as positive pole, the capacity of being assembled into is the 055570 type flexible-packed battery of 1Ah, then at 55 DEG C, carries out loop test, and test the cycle life of full battery 80%, test result is as shown in table 2:
Table 2
In addition, by the full cycle performance of battery comparison diagram of positive electrode in gained final products in embodiment 1 and comparative example 1, as shown in Figure 6, can learn:
The curve that the battery be made up of embodiment 1 gained positive electrode obtains is compared to the curve obtained by comparative example 1, and at high temperature, cycle-index is many, and repeatedly after circulation, conservation rate is high, and therefore, positive electrode provided by the invention has excellent cycle performance.
More than in conjunction with embodiment and exemplary example to invention has been detailed description, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that when not departing from spirit and scope of the invention, can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and execution mode thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.

Claims (9)

1. a power lithium-ion battery high-temperature manganic acid lithium cathode material, this positive electrode comprises with lower part:
Core and
Coating layer,
Wherein, described core is by shown in formula I:
Li 1+xMn 2-y-zA yQ zO 4
Formula I
In described formula I, metal element A be selected from Al, Mg, Co one or more, metallic element Q be selected from Al, Mg, Co, Nb, Cr one or more,
In described formula I, 0≤x≤0.2,0<y≤0.18,0<z≤0.1, and, 0<y+z≤0.2,1≤y/z≤10,
Described coating layer is at described core surfaces, described coating layer is one or more in cobaltosic oxide, alundum (Al2O3), nickel protoxide, and in coating layer, the mole sum of metallic element is metallic element with the ratio of the mole of core: core=0.003 ~ 0.15:1.
2. positive electrode according to claim 1, wherein, in described coating layer, the mole sum of metallic element is metallic element with the ratio of the mole of core: core=0.015 ~ 0.09:1, or/and described metallic element Q is the combination of Al, Cr or Mg and Nb, or/and 0.1≤x≤0.2, or/and 0.05≤y+z≤0.15, or/and 1≤y/z≤3.
3. positive electrode according to claim 1 and 2, wherein, described positive electrode is spheric granules, and the meso-position radius of the positive electrode of form of spherical particles is 5 ~ 20 microns, preferably 8 ~ 12 microns.
4. prepare a method for the positive electrode according to any one of claims 1 to 3, the method comprises the following steps:
The preparation of the presoma of step one, positive electrode:
1) soluble-salt of manganese being mixed with mixed aqueous solution with the soluble-salt containing elements A joins in reactor, the total mol concentration of mixed aqueous solution is 1 ~ 3mol/l, control the soluble-salt of manganese and the rate of charge of the soluble-salt containing metal element A, make the manganese element in the soluble-salt of manganese and be Mn:A=(2-y-z): y containing the mol ratio of metal element A in the soluble-salt of metal element A, 0<y≤0.18,0<z≤0.1, and, 0<y+z≤0.2,1≤y/z≤10
Wherein, the soluble-salt of manganese be selected from manganese sulfate, manganese nitrate one or more, the soluble-salt containing metal element A be selected from sulfate containing metal element A, nitrate, hydrochloride one or more, described metal element A is Al, Mg and Co,
2) under agitation, to step 1) described in reactor in respectively add sodium hydrate aqueous solution and ammonia spirit simultaneously, react 6 ~ 20 hours, simultaneously, the pH of the hierarchy of control is 8 ~ 10, the reaction temperature of system is 40 ~ 60 DEG C, now constantly precipitates the coprecipitate that output contains the hydroxide of manganese element and metal element A
Wherein, the concentration of sodium hydrate aqueous solution is 1 ~ 5mol/l, and the concentration of ammonia spirit is 1 ~ 5mol/l, and sodium hydrate aqueous solution and ammonia spirit charging rate are than being 3:1 ~ 2:1.
3) by step 2) in the coprecipitate that obtains dry at 100 ~ 120 DEG C, obtain the bulk phase-doped spherical mangano-manganic oxide having metal element A, i.e. the presoma of positive electrode;
Step 2, preparation by the core shown in formula I:
1) by gained presoma in step one, mix with lithium source and the oxide containing metallic element Q, grind, mix, its rate of charge is the mole of the element A made in presoma, the ratio of the mole of Q element in Li element mole in lithium source, oxide containing metallic element Q is A:Li:Q=y:(1+x): z, 0≤x≤0.2,0<y≤0.18,0<z≤0.1, and, 0<y+z≤0.2,1≤y/z≤10
Wherein, lithium source is one or more in lithium carbonate, lithium hydroxide and lithium nitrate, and the oxide containing metallic element Q is containing one or more in the oxide of Al, Mg, Co, Nb, Cr,
2) by step 1) in the roasting 5 ~ 30 hours at 600 ~ 900 DEG C of the mixture that mixes, be then cooled to 500 DEG C with the speeds control of 1 ~ 2 DEG C/min and continue roastings, after roasting completes, cooling, pulverizes, and screening, obtains by the core shown in formula I,
The preparation of step 3, positive electrode:
1) mix by the core shown in formula I with the additive M containing metallic element, rate of charge is make the mole of additive M containing metallic element be M:O=0.001 ~ 0.05:1 with the ratio of the mole of core,
Wherein, the additive M containing metallic element is one or more in cobalt carbonate, cobalt hydroxide, aluminium powder, nickel protoxide, and the median of described additive is less than 3 microns,
2) by step 1) in mixture heat treatment 2 ~ 15h at the temperature of 400 ~ 800 DEG C of mixing, cooling, after screening, obtains positive electrode, i.e. power lithium-ion battery high-temperature manganic acid lithium cathode material.
5. method according to claim 4, wherein, in the preparation of the presoma of described positive electrode:
In described step 1) in, 0.05≤y+z≤0.15, or/and 1≤y/z≤3, or/and be selected from one or more in sulfate containing metal element A, nitrate containing the soluble-salt of metal element A, or/and the speed that adds of mixed aqueous solution is 0.5 ~ 3ml/min, the speed that adds of ammonia spirit is 0.3 ~ 1ml/min, or/and the reaction temperature of system is 50 ~ 60 DEG C
In described step 2) in, after reaction terminates, continue ageing 4 ~ 10 hours, or be 1100 ~ 1500r/min with stir speed (S.S.).
6. method according to claim 4, wherein, in the preparation of described core:
In described step 1) in, 0.1≤x≤0.2, or/and 0.05≤y+z≤0.15, or/and 1≤y/z≤3, or/and the oxide containing metallic element Q is one or more in aluminium oxide, magnesium oxide, chromium oxide and niobium pentaoxide.
7. method according to claim 4, wherein, in the preparation of described positive electrode:
In described step 1) in, the mole of additive M containing metallic element is M:O=0.005 ~ 0.03:1 with the ratio of the mole of core, or/and the additive M containing metallic element is one or more in cobalt carbonate, cobalt hydroxide, nanometer aluminium powder, nickel protoxide
In described step 2) in, when heat treated temperature is greater than 500 DEG C, then after heat treatment, system is cooled to 500 DEG C with the rate of temperature fall of 1 ~ 2 DEG C/min by system, then continues heat treatment.
8. method according to any one of claim 4 ~ 7, wherein,
The meso-position radius of the presoma of described positive electrode is 5 ~ 15 microns, is preferably 8 ~ 10 microns;
The described meso-position radius by the core shown in formula I is 5 ~ 20 microns, is preferably 8 ~ 12 microns;
The meso-position radius of described positive electrode is 5 ~ 20 microns, is preferably 8 ~ 12 microns.
9. the high-temperature manganic acid lithium cathode material of the power lithium-ion battery according to any one of claim 1 ~ 8 is used for the purposes of power lithium-ion battery positive electrode.
CN201410843002.7A 2014-12-30 2014-12-30 A kind of power lithium-ion battery high-temperature manganic acid lithium cathode material and preparation method thereof Active CN104485452B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410843002.7A CN104485452B (en) 2014-12-30 2014-12-30 A kind of power lithium-ion battery high-temperature manganic acid lithium cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410843002.7A CN104485452B (en) 2014-12-30 2014-12-30 A kind of power lithium-ion battery high-temperature manganic acid lithium cathode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104485452A true CN104485452A (en) 2015-04-01
CN104485452B CN104485452B (en) 2016-08-24

Family

ID=52759975

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410843002.7A Active CN104485452B (en) 2014-12-30 2014-12-30 A kind of power lithium-ion battery high-temperature manganic acid lithium cathode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104485452B (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105374996A (en) * 2015-09-23 2016-03-02 彩虹集团电子股份有限公司 Method for treatment on high-voltage Ni-Co-Mn ternary positive electrode material by surface drying method
CN106532006A (en) * 2016-12-16 2017-03-22 无锡晶石新型能源有限公司 Preparation method of cobaltous oxide coated ternary anode material
CN106784795A (en) * 2017-01-16 2017-05-31 湖南瑞翔新材料股份有限公司 A kind of spherical lithium manganate material of monocrystalline and preparation method thereof, positive electrode
CN107887598A (en) * 2017-10-31 2018-04-06 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of alkali metal ion doping tertiary cathode material and products thereof and application
CN109478645A (en) * 2016-07-14 2019-03-15 三井金属矿业株式会社 Fully solid positive active material for lithium secondary battery
CN109560284A (en) * 2018-11-06 2019-04-02 山西北斗星新材料有限公司 A kind of high performance doping type lithium manganate positive electrode and preparation method thereof
CN109562342A (en) * 2016-06-23 2019-04-02 阿玛斯坦技术有限公司 Lithium ion battery material
CN110061225A (en) * 2019-05-06 2019-07-26 湖南金富力新能源股份有限公司 A kind of monocrystalline high capacity nickel-cobalt lithium manganate cathode material and preparation method thereof
CN110112371A (en) * 2018-02-01 2019-08-09 天津国安盟固利新材料科技股份有限公司 A kind of method of surface coating modification Spinel positive electrode
CN111509219A (en) * 2020-04-13 2020-08-07 江门市科恒实业股份有限公司 Lithium manganate battery material and preparation method thereof
CN112390292A (en) * 2020-11-13 2021-02-23 贵州大龙汇成新材料有限公司 Bulk phase doped manganous-manganic oxide and preparation method and application thereof
US11273491B2 (en) 2018-06-19 2022-03-15 6K Inc. Process for producing spheroidized powder from feedstock materials
US11311938B2 (en) 2019-04-30 2022-04-26 6K Inc. Mechanically alloyed powder feedstock

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103794763A (en) * 2014-03-03 2014-05-14 中信国安盟固利电源技术有限公司 Lithium ion cell anode material coated with nanometer metal and manufacturing method of lithium ion cell anode material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103794763A (en) * 2014-03-03 2014-05-14 中信国安盟固利电源技术有限公司 Lithium ion cell anode material coated with nanometer metal and manufacturing method of lithium ion cell anode material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DONGSHENG GUAN, ET AL.: ""Enhanced cycleability of LiMn2O4 cathodes by atomic layer deposition of nanosized-thin Al2O3 coatings"", 《NANOSCALE》 *
JAEPHIL CHO ET AL.: ""Complete blocking of Mn3+ ion dissolution from a LiMn2O4 spinel intercalation compound by Co3O4 coating"", 《CHEM. COMMUN.》 *
张瑾瑾等: ""三氧化二铝包覆锂离子电池用尖晶石锰酸锂"", 《电池》 *
蒋庆来: ""浆料喷雾干燥法制备球形锰酸锂正极材料及其改性研究"", 《中国博士学位论文全文数据库 工程科技II辑》 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105374996A (en) * 2015-09-23 2016-03-02 彩虹集团电子股份有限公司 Method for treatment on high-voltage Ni-Co-Mn ternary positive electrode material by surface drying method
CN109562342B (en) * 2016-06-23 2022-08-12 6K有限公司 Lithium ion battery material
CN109562342A (en) * 2016-06-23 2019-04-02 阿玛斯坦技术有限公司 Lithium ion battery material
CN109478645A (en) * 2016-07-14 2019-03-15 三井金属矿业株式会社 Fully solid positive active material for lithium secondary battery
CN106532006A (en) * 2016-12-16 2017-03-22 无锡晶石新型能源有限公司 Preparation method of cobaltous oxide coated ternary anode material
CN106784795A (en) * 2017-01-16 2017-05-31 湖南瑞翔新材料股份有限公司 A kind of spherical lithium manganate material of monocrystalline and preparation method thereof, positive electrode
CN106784795B (en) * 2017-01-16 2020-04-24 湖南瑞翔新材料股份有限公司 Single-crystal spherical lithium manganate material, preparation method thereof and positive electrode material
CN107887598A (en) * 2017-10-31 2018-04-06 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of alkali metal ion doping tertiary cathode material and products thereof and application
CN110112371A (en) * 2018-02-01 2019-08-09 天津国安盟固利新材料科技股份有限公司 A kind of method of surface coating modification Spinel positive electrode
US11273491B2 (en) 2018-06-19 2022-03-15 6K Inc. Process for producing spheroidized powder from feedstock materials
US11465201B2 (en) 2018-06-19 2022-10-11 6K Inc. Process for producing spheroidized powder from feedstock materials
US11471941B2 (en) 2018-06-19 2022-10-18 6K Inc. Process for producing spheroidized powder from feedstock materials
CN109560284A (en) * 2018-11-06 2019-04-02 山西北斗星新材料有限公司 A kind of high performance doping type lithium manganate positive electrode and preparation method thereof
US11311938B2 (en) 2019-04-30 2022-04-26 6K Inc. Mechanically alloyed powder feedstock
CN110061225A (en) * 2019-05-06 2019-07-26 湖南金富力新能源股份有限公司 A kind of monocrystalline high capacity nickel-cobalt lithium manganate cathode material and preparation method thereof
CN110061225B (en) * 2019-05-06 2020-09-15 湖南金富力新能源股份有限公司 Single-crystal high-capacity nickel cobalt lithium manganate positive electrode material and preparation method thereof
CN111509219A (en) * 2020-04-13 2020-08-07 江门市科恒实业股份有限公司 Lithium manganate battery material and preparation method thereof
CN111509219B (en) * 2020-04-13 2022-04-15 江门市科恒实业股份有限公司 Lithium manganate battery material and preparation method thereof
CN112390292A (en) * 2020-11-13 2021-02-23 贵州大龙汇成新材料有限公司 Bulk phase doped manganous-manganic oxide and preparation method and application thereof

Also Published As

Publication number Publication date
CN104485452B (en) 2016-08-24

Similar Documents

Publication Publication Date Title
CN104485452A (en) High-temperature type lithium manganate anode material for power lithium ion battery and preparation method of high-temperature type lithium manganate anode material
JP5712544B2 (en) Positive electrode active material particle powder, method for producing the same, and nonaqueous electrolyte secondary battery
CN103972499B (en) A kind of nickel cobalt lithium aluminate cathode material of modification and preparation method thereof
CN103715424A (en) Core-shell structured cathode material and preparation method thereof
Zhang et al. An improved carbonate co-precipitation method for the preparation of spherical Li [Ni1/3Co1/3Mn1/3] O2 cathode material
CN102983326B (en) Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN104037401B (en) Nickel-cobalt-lithium manganate ternary anode material suitable for application under high voltage
CN105870438B (en) A kind of lithium secondary battery lithium-rich anode composite material and preparation method
CN106299295B (en) A kind of porous micro-nano structure lithium-enriched cathodic material of lithium ion battery and preparation method thereof with shuttle shape pattern
CN102583583B (en) A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof
WO2015039490A1 (en) Lithium-rich anode material and preparation method thereof
CN106299255B (en) A kind of preparation method of big partial size spinel-type nickel ion doped
Gao et al. Synthesis and electrochemical performance of long lifespan Li-rich Li1+ x (Ni0. 37Mn0. 63) 1− xO2 cathode materials for lithium-ion batteries
CN110380024A (en) Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery
Liang et al. Synthesis and electrochemical performance of LiNi0. 6Co0. 2Mn0. 2O2 as a concentration-gradient cathode material for lithium batteries
CN103872302A (en) Lithium ion battery positive pole material precursor and its preparation method
CN108365216A (en) The novel nickelic tertiary cathode material of one kind and preparation
Jiang et al. A design strategy of large grain lithium-rich layered oxides for lithium-ion batteries cathode
CN103078099A (en) Anode material for lithium ion cell and preparation method thereof
CN104779385A (en) High-specific capacity lithium ion battery cathode material and preparation method thereof
CN103606675A (en) Preparation method of metallic-ion-doped lithium-nickel-cobalt-oxygen positive pole material
CN103187566B (en) Tubular lithium-rich anode material, preparation method and application thereof
Ma et al. Effect of metal ion concentration in precursor solution on structure and electrochemical performance of LiNi0. 6Co0. 2Mn0. 2O2
Wang et al. Surface modification of Li rich Li1. 2Mn0. 54Ni0. 13Co0. 13O2 cathode particles
CN106910887A (en) A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode

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: 102200 Beijing city Changping District Bai Fu Road 18

Patentee after: Beijing mengguli New Material Technology Co.,Ltd.

Address before: 102200 No. 18, baifuquan Road, Changping District, Beijing

Patentee before: CITIC GUOAN MENGGULI POWER SOURCE TECHNOLOGY Co.,Ltd.

CP03 Change of name, title or address