CN103762354A - LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery - Google Patents

LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery Download PDF

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CN103762354A
CN103762354A CN201410028686.5A CN201410028686A CN103762354A CN 103762354 A CN103762354 A CN 103762354A CN 201410028686 A CN201410028686 A CN 201410028686A CN 103762354 A CN103762354 A CN 103762354A
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manganese dioxide
lithium ion
ion battery
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CN103762354B (en
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刘军
唐莎莎
季文海
闵杰
梁叔全
唐艳
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a LiNi0.5Mn1.5O4 material, a preparation method thereof as well as a lithium ion battery. The method comprises the following steps: preparing a superfine manganese dioxide nanowire by adopting a hydrothermal method, uniformly mixing a manganese dioxide nanowire precursor with a lithium salt and a nickel salt according to a certain ratio, calcining in air to obtain a LiNi0.5Mn1.5O4 nanorod which is uniform in distribution and small in size. The used raw materials are low in price, the environmental pollution is avoided, and the process is easily controlled and suitable for large-scale industrial production. The lithium ion battery made of an anode material prepared by the method has the discharge specific energy of more than 480Wh Kg<-1>, and when the charge and discharge frequency is 500 times, the capacity retention ratio and efficiency are kept over 99%.

Description

A kind of LiNi 0.5mn 1.5o 4material, its preparation method and lithium ion battery
Technical field
The present invention relates to lithium ion battery field, be specifically related to a kind of LiNi 0.5mn 1.5o 4material, its preparation method and lithium ion battery.
Background technology
In the face of the challenge of energy problem, development heavy-duty battery can be alleviated predicament effectively.Existing chargeable battery has lead-acid battery, nickel-cadmium cell, Ni-MH battery and the large class of lithium ion battery four.Under this background, lithium ion battery is as one of chemical energy storage device, have that operating voltage is high, energy density is high, have extended cycle life, the many advantages such as memory-less effect, self-discharge rate are low, green non-pollution, become the object that national governments and researcher pay close attention to.The application of lithium ion battery at present has extended to the every aspect of people's life, and small-scale lithium ion cell is for aspects such as communication apparatus, household electrical appliance, electronic product, fire-fighting illuminations, and large-sized battery is mainly used in peak load regulation network, power vehicle etc.But along with the rapid growth of the flourish of electronic information technology and clean energy resource demand, there have been requirements at the higher level the aspects such as energy density, stability, useful life, fail safe and the cost of people to lithium ion battery, make high performance lithium ion battery become the research and development focus of new century.Useful life, security performance and the energy of lithium ion battery, power density are the important parameter of evaluating its performance.The cyclic reversibility of lithium ion battery has determined its useful life, and capacity and operating voltage have determined the energy density of battery, and higher operating voltage is also beneficial to the lifting of power of battery density.So high working voltage is not only beneficial to raising, battery miniaturization and the lightness of battery performance, and can reduce the assembling quantity of cell in battery pack, be beneficial to and economize on resources and reduce costs.
Current commercial anode material for lithium ion battery all exists some shortcomings, as commercial layered cathode material LiCoO 2although be used widely in compact battery, but cobalt is expensive, toxic, it overcharges insecurity and makes cycle performance poor, thereby limited its be applied (J.R.Ying, C.Y.Jiang, C.R.Wan in high capacity cell, Journal of Power Sources, 2004,129,264); Spinelle LiMn 2o 4(theoretical capacity: 148mAh/g) is lower than the former cost, security performance is higher; but the shortcoming that its capacity is low and high temperature cyclic performance is poor is also limiting its utilization (E.Hosono always; T.Kudo; I.Honma, H.Matsuda, H.S.Zhou; Nano Letters; 2009,9,1045); There is the LiFePO of olivine-type structure 4(theoretical capacity: 170mAh/g) can reversibly embed and removal lithium embedded ion, and environmental protection, cheap, good cycle promise to be the desirable positive electrode of lithium ion battery.But because of its poorly conductive, be not suitable for high current charge-discharge, also limited its utilization (G.X.Wang, H.Liu, J.Liu, S.Z.Qiao, G.M.Lu, P.Munro, H.Ahn, Advanced Materials, 2010,22,4944).
Than current these commercial positive electrode LiCoO 2, LiMn 2o 4, LiFePO 4deng, spinel-type LiNi 0.5mn 1.5o 4material has that three-dimensional ion diffusion admittance, discharge voltage are high, Stability Analysis of Structures, aboundresources, cost are low and advantages of environment protection and become one of focus material of current research.Particularly it,, at the high potential discharge platform of 4.8V left and right, under same current, can provide higher energy, power density, simultaneously Ni 2+after ion doping, can suppress Manganic ion formation, alleviate material capacity decay serious problem, promote cycle performance, and then all required very harsh electrical source of power used for electric vehicle field to favor to power supply capacity, battery life and use safety, become one of alternative positive electrode of lithium ion battery of new generation, thereby enjoy the concern of various countries' researcher.But LiNi 0.5mn 1.5o 4positive electrode is when charged state, and the transition metal ions of high oxidation state is understood oxidation electrolyte, and in electrolyte, contained a small amount of acidic materials will corrode positive electrode.Thereby the side reaction between positive electrode and electrolyte causes its discharge capacity seriously to decay.Therefore for realizing LiNi 0.5mn 1.5o 4material is commercialization early, improves its cycle performance (capability retention) imperative.In recent years, some seminars have started to have carried out LiNi in the world 0.5mn 1.5o 4the research of material is mainly by improvement, to prepare synthetic method to improve its actual specific capacity, cyclical stability and high rate performance.Such as solid reaction process, sol-gal process and coprecipitation etc.: the people such as Sun prepare LiNi by two step solid phase methods 0.5mn 1.5o 4material is made after battery, and under the condition of 0.1C multiplying power charging and 0.2C multiplying power discharging, the capability retention after 30 times that circulates is 96%, but by solid reaction process, need at high temperature calcining for a long time, power consumption is large, and material prepared by solid phase method is easily reunited, particle scale cannot regulate and control and poor (the Sun Q of homogeneity, Li X H, Wang Z X, et al, Transactions of Nonferrous Metals Society of China, 2009,19,176-181); The people such as Yang have prepared LiNi with ultrasonic auxiliary sol-gal process 0.5mn 1.5o 4material, the structural stability of its material strengthen and particle more orderly, the capability retention after 50 times that circulates under 0.2C discharge-rate is 96%.But this preparation method's operating procedure is more, with a certain distance from large-scale production, also have (Sun Y Y, Yang Y F, Zhan H, et al, Journal of Power Sources, 2010,195 (13): 4322-4326); Coprecipitation can, by changing particle diameter and the pattern of technological parameter regulation and control product, be conducive to improve the chemical property of material.But this method difficult point is accurately to control the settling rate of each component, and how at molecular level, to form uniform multicomponent precipitation.
In addition, existing positive electrode, when charged state, the transition metal ions meeting oxidation electrolyte of high oxidation state, and contained a small amount of acidic materials will corrode positive electrode in electrolyte, thereby the discharge capacity of battery is seriously decayed, cyclical stability is poor.As spinelle LiMn 2o 4, in charging process, can there is the manganese ion of disproportionated reaction generation divalence and tetravalence in Manganic ion, and divalent manganesetion can be dissolved in electrolyte, the dissolving gradually of electrode material has aggravated the decay of battery capacity, and cyclical stability is poor.
Summary of the invention
The present invention is directed under high pressure existing positive electrode LiNi 0.5mn 1.5o 4the transition metal ions of high oxidation state meeting oxidation electrolyte under Charging state, and in electrolyte, contained a small amount of acidic materials can corrode positive electrode, thus the discharge capacity of battery is seriously decayed, the present situation that cyclical stability is poor, from improving in essence LiNi 0.5mn 1.5o 4removal lithium embedded cyclical stability, provide a kind of high at the lower electric discharge of high pressure (more than being specifically greater than the voltage of 4V) specific energy, capability retention is high, the LiNi of good cycle, long service life 0.5mn 1.5o 4material.
Another object of the present invention is to provide a kind of relative prior art preparation method simple, be applicable to the LiNi of suitability for industrialized production 0.5mn 1.5o 4the preparation method of material.
Another object of the present invention is to LiNi 0.5mn 1.5o 4material is applied in lithium ion battery as positive pole, obtains the lithium ion battery with high cyclical stability and high-energy-density.
Technical scheme of the present invention
A kind of LiNi 0.5mn 1.5o 4material, described LiNi 0.5mn 1.5o 4for nanorod structure, its diameter is 30nm-50nm, and length is 1 μ m-5 μ m.
LiNi of the present invention 0.5mn 1.5o 4material prepares by the following method: after manganese sulphate powder and potassium permanganate powder are dissolved in deionized water, stirring, (solution obtaining is aubergine, then this solution is poured in the reactor of polytetrafluoroethylliner liner), reaction at 150-160 ℃, washing impurity-removing, dry, obtains manganese dioxide nano line presoma; By above-mentioned manganese dioxide nano line presoma, nickel nitrate, lithium hydroxide, according to the mol ratio of Mn: Ni: Li, it is 1.5: 0.5: the mixture of powders of 1.05-1.06 is dissolved in absolute ethyl alcohol, stirring at room, dry, grind, after calcining, obtain product at 780-820 ℃.
The diameter of the manganese dioxide nano line presoma that the present invention obtains is 5-10nm, and length is 1-5 μ m.
The described reaction time at 150-160 ℃ is preferably 10-12h.
The described stirring at room time is preferably 24-36h.
Described calcining is preferably in air and is warming up to 780-820 ℃ with the heating rate of 5-10 ℃/min.After being warmed up to 780-820 ℃, constant temperature 20-24h is advisable.If heating rate is greater than 10 ℃/min, be difficult to keep the linear looks of manganese dioxide nano, very easily generate inhomogeneous LiNi 0.5mn 1.5o 4particle.
Described mixture is preferably hand-ground 10 minutes.
By above-mentioned LiNi 0.5mn 1.5o 4material is as the lithium ion battery of positive electrode.
Effect of the present invention
Use the undersized nano bar-shape LiNi of structure of the present invention 0.5mn 1.5o 4during material, active material fully contacts with electrolyte, and the avtive spot of removal lithium embedded increases, and lithium ion the evolving path shortens greatly, and this has promoted the raising of positive electrode chemical property greatly.Use LiNi of the present invention 0.5mn 1.5o 4material, high (the 480Wh Kg of the specific energy that under high pressure discharges -1capability retention high (while discharging and recharging 500 times, capability retention and efficiency all remain on more than 99%), good cycle, long service life above).And LiNi of the present invention 0.5mn 1.5o 4the preparation method of material is simple, reaction condition gentleness, and environmental friendliness, production cost is low, is suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is manganese dioxide presoma and LiNi prepared by embodiment 1 0.5mn 1.5o 4x ray diffracting spectrum;
Wherein Fig. 1 (a) is undersized LiNi 0.5mn 1.5o 4the X ray diffracting spectrum of nanometer rods, the diffraction maximum of the nanometer rods as can be seen from the figure obtaining is consistent with PDF card ICDD-PDF80-2162, and synthetic LiNi is described 0.5mn 1.5o 4belong to cubic system.
Fig. 1 (b) is the X ray diffracting spectrum of superfine manganese dioxide nano line, and as can be seen from the figure the diffraction maximum of nano wire is consistent with PDF card ICDD-PDF44-0141, illustrates that synthetic manganese dioxide is tetragonal crystal system.According to X-ray diffraction principle, diffraction maximum is wider, and the granularity of the material of surveying is less, and the diffraction maximum of nano wire is wider than the diffraction maximum of nanometer rods, illustrates that the yardstick of manganese dioxide presoma nano wire is less than LiNi 0.5mn 1.5o 4the yardstick of nanometer rods, this is consistent with the result of Fig. 2 and Fig. 3.
Fig. 2 is manganese dioxide nano line presoma ESEM and transmission electron microscope photo prepared by embodiment 1;
As can be seen from the figure the manganese dioxide that prepared by the present invention is nanometer wire pattern, and diameter is 5-10nm, and length is 1-5 μ m, and many nano wires flock together, and forms one by one diameter in 50nm left and right, the collective of length 1-5 μ m.
Fig. 3 is the LiNi of preparation in embodiment 1 0.5mn 1.5o 4transmission electron microscope photo;
As can be seen from the figure the LiNi that, prepared by the present invention 0.5mn 1.5o 4be nano bar-shape pattern, diameter is in 30-50nm left and right, and length is 1-5 μ m, has kept the pattern of manganese dioxide nano line collective in presoma.
Fig. 4 is LiNi prepared by embodiment 1 0.5mn 1.5o 4the chemical property figure of electrode material.
Fig. 4 (a) and (b) be to use the LiNi for preparing of the embodiment of the present invention 1 0.5mn 1.5o 4the cyclic voltammetry curve of the lithium ion battery that material is made and simple charging and discharging curve.
The specific discharge capacity that circulates for the first time declines, this is because circulation has formed solid electrolyte passivating film for the first time, can see after circulation for the second time, curve is almost overlapping, the redox reaction degree of reversibility that this explanation battery material charge and discharge process occurs is high, and this is an important factor in order of good cycling stability.
From Fig. 4 (c), can find out the LiNi that uses the embodiment of the present invention 1 to prepare 0.5mn 1.5o 4the lithium ion battery that material is made 500 times time, still keeps 480Wh Kg in circulation -1electric discharge specific energy, efficiency is up to 99%, and the LiNi of commodity in use 0.5mn 1.5o 4the specific energy that discharges after the lithium ion battery circulation of making 50 times just quickly falls to 220Wh Kg -1left and right, illustrates that nanometer rods pattern is conducive to improve the cyclical stability of lithium ion battery.
From Fig. 4 (d), can find out the LiNi that uses the embodiment of the present invention 1 to prepare 0.5mn 1.5o 4the electrochemical impedance of the lithium ion battery that material is made only has 200 Ω, and the LiNi of commodity in use 0.5mn 1.5o 4the electrochemical impedance of the lithium ion battery of making, up to 350 Ω, illustrates LiNi of the present invention 0.5mn 1.5o 4nano-bar material is conducive to improve the conductivity of lithium ion battery.
Embodiment
Below in conjunction with embodiment, be intended to further illustrate the present invention, and unrestricted the present invention.
Embodiment 1
After manganese sulphate powder and potassium permanganate powder are dissolved in deionized water, stir and obtain purplish red solution; Then solution is poured into the reactor of polytetrafluoroethylliner liner, add thermal response, use deionized water and absolute ethyl alcohol centrifuge washing three times, remove after the foreign ion that may contain in this presoma, be placed in 60 ℃ of air dry ovens dry, obtain superfine manganese dioxide nano line presoma; Weigh manganese dioxide presoma and nickel nitrate and lithium hydroxide powder, wherein manganese dioxide presoma, nickel nitrate, lithium hydroxide three's mol ratio is 1.5: 0.5: 1.05-1.06, the mixture of three's powder is dissolved in 15mL absolute ethyl alcohol, stirring at room is to dry, grind again 10 minutes, in air, calcine, obtain uniform LiNi 0.5mn 1.5o 4nanometer rods.
Embodiment 2
By the manganese dioxide presoma in embodiment 1, nickel nitrate, lithium hydroxide three's mol ratio, it is 1.5: 0.5: 1-1.04, other synthesis conditions remain unchanged to prepare LiNi 0.5mn 1.5o 4nano material.
Result cannot be synthesized LiNi 0.5mn 1.5o 4material.
Embodiment 3
The time shorten that manganese dioxide presoma in embodiment 1, nickel nitrate, lithium hydroxide three mixture are calcined in air is 10-15h, and other synthesis conditions remain unchanged to prepare LiNi 0.5mn 1.5o 4nano material.
Result shortens the calcination reaction time cannot synthesize LiNi 0.5mn 1.5o 4material.
Embodiment 4
Do not use the manganese dioxide nano line presoma in embodiment 1, alternative with commercial manganese dioxide particle, other synthesis conditions remain unchanged to prepare LiNi 0.5mn 1.5o 4nano material.
Result cannot be synthesized the LiNi of pure phase under same condition 0.5mn 1.5o 4material.
Electrochemical property test
LiNi prepared by embodiment 1 0.5mn 1.5o 4material, after acetylene black and polyvinylidene fluoride (PVDF) binding agent mixes according to the weight ratio of 7:2:1, is dispersed in 1-METHYLPYRROLIDONE (NMP) solution and obtains starchy mixture.The paste mixture obtaining is coated on aluminium foil, and spends the night 90 ℃ of vacuumizes.Li/LiNi 0.5mn 1.5o 4being assembled in the glove box (Mbraum, Germany) of having filled high-purity argon gas of button cell (2016 model) carried out.
Using metal lithium sheet as negative pole, using polypropylene screen as barrier film, 1M LiPF 6be dissolved in ethyl carbonate/dimethyl carbonate (EC/DMC) (1:1, volume ratio) as electrolyte, the synthetic LiNi that contains 0.5mn 1.5o 4the pole piece of material is as the positive electrode of battery.The charging and discharging performance test of lithium ion battery is carried out under room temperature in blue electrical testing system, and the voltage range of test is 3.5-5.0V reference and Li/Li +.Cyclic voltammetry carries out in IM6ex electrochemical workstation system, and test rate is 0.1mV s -1.
Table 1 is LiNi prepared by the embodiment of the present invention 1 0.5mn 1.5o 4material and the contrast of other anode material for lithium-ion batteries chemical property.Therefrom visible, prepared by the present invention LiNi 0.5mn 1.5o 4the positive electrode of the energy of electrode material and other kinds of capability retention geometric ratio is higher, and cycle life is longer; With respect to list of references 1(M.V.Reddy, H.Y.Cheng, J.H.Tham, C.Y.Yuan, H.L.Goh, B.V.R.Chowdari, Electrochim.Acta, 2012,62,269-275.) and the LiNi for preparing of application number 201310302143.3 0.5mn 1.5o 4material, nanometer rods sample capacity conservation rate prepared by this method is up to 99%.
Figure BDA0000460120670000061

Claims (9)

1. a LiNi 0.5mn 1.5o 4material, is characterized in that, described LiNi 0.5mn 1.5o 4for nanorod structure, its diameter is 30nm-50nm, and length is 1 μ m-5 μ m.
2. material according to claim 1, is characterized in that, described LiNi 0.5mn 1.5o 4material is prepared by the following method: after manganese sulphate powder and potassium permanganate powder are dissolved in deionized water, stirs, and reaction at 150-160 ℃, washing, dry, obtains manganese dioxide nano line presoma; The mixture of powders that is 1.5: 0.5: 1.05～1.06 according to the mol ratio of Mn: Ni: Li by above-mentioned manganese dioxide nano line presoma, nickel nitrate, lithium hydroxide is dissolved in absolute ethyl alcohol, at stirring at room, dry, grinding, 780-820 ℃, after calcining, obtains product.
3. a LiNi 0.5mn 1.5o 4the preparation method of material, after manganese sulphate powder and potassium permanganate powder are dissolved in deionized water, stirs, reaction at 150-160 ℃, and washing, dry, obtains manganese dioxide nano line presoma; The mixture of powders that is 1.5: 0.5: 1.05～1.06 according to the mol ratio of Mn: Ni: Li by above-mentioned manganese dioxide nano line presoma, nickel nitrate, lithium hydroxide is dissolved in absolute ethyl alcohol, at stirring at room, dry, grinding, 780-820 ℃, after calcining, obtains product.
4. preparation method according to claim 3, is characterized in that, the diameter of described manganese dioxide nano line presoma is 5nm-10nm, and length is 1 μ m-5 μ m.
5. preparation method according to claim 3, is characterized in that, the described reaction time at 150-160 ℃ is 10-12h.
6. preparation method according to claim 3, is characterized in that, the described stirring at room time is 24-36h.
7. preparation method according to claim 3, is characterized in that, described calcining is with the heating rate of 5-10 ℃/min, to be warming up to 780-820 ℃ of calcining in air.
8. preparation method according to claim 7, is characterized in that, is warming up to after 780-820 ℃, and constant temperature keeps 20-24h.
9. with the LiNi described in claim 1-8 any one 0.5mn 1.5o 4material is as the lithium ion battery of positive electrode.
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CN104966830A (en) * 2015-05-25 2015-10-07 哈尔滨工业大学 Preparation method and application of rod-shaped lithium nickel manganese oxide material
CN107256964A (en) * 2017-06-14 2017-10-17 哈尔滨工业大学（威海） A kind of preparation method of the bar-shaped nickel ion doped of high-voltage lithium-battery cathode material
CN111087030A (en) * 2019-12-20 2020-05-01 佛山科学技术学院 LiNi0.5Mn1.5O4Method for producing materials and use thereof
CN112928244A (en) * 2019-12-05 2021-06-08 济南圣泉集团股份有限公司 Lithium ion battery electrode material, preparation method and battery
CN113165905A (en) * 2018-12-19 2021-07-23 托普索公司 Lithium positive electrode active material
CN114195201A (en) * 2021-12-10 2022-03-18 合肥国轩高科动力能源有限公司 Preparation method of long-life cobalt-free cathode material
CN114275827A (en) * 2021-12-16 2022-04-05 河源职业技术学院 Method for preparing ternary composite material by using manganese dioxide nanorod precursor
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