CN104091919A - Positive electrode material for lithium ion battery and preparation method of positive electrode material - Google Patents

Positive electrode material for lithium ion battery and preparation method of positive electrode material Download PDF

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CN104091919A
CN104091919A CN201410365645.5A CN201410365645A CN104091919A CN 104091919 A CN104091919 A CN 104091919A CN 201410365645 A CN201410365645 A CN 201410365645A CN 104091919 A CN104091919 A CN 104091919A
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manganese
positive electrode
lithium
preparation
potassium
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CN104091919B (en
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李莉萍
李琪
付超超
李广社
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a potassium-doped rich-lithium manganese-based oxide positive electrode material and a preparation method of the positive electrode material. The chemical formula of the positive electrode material can be expressed as Li<(3+x)/3-y>K<y>Mn<(1+x)/3>Co<(1-x)/3>Ni<(1-x)/3>O2, wherein x is greater than or equal to 0.3, and less than or equal to 0.9, and y is equal to (1+x)/162. The positive electrode material has extremely high energy density and excellent cycle performance and rate performance. An in-situ potassium-doped manganese precursor is taken as a manganese source for preparing the positive electrode material; the adopted preparation method has the advantages of simple operation, low production cost, short synthesis period, high repeatability and the like, and can be widely applied to the synthesis of the oxide positive electrode materials for the lithium ion batteries.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field
The application relates to a kind of original position potassium in lithium ion battery field lithium-rich manganese-based oxide anode material and preparation method thereof that adulterates.
Background technology
Lithium-rich manganese-based tertiary cathode material, because its high specific discharge capacity has been subject to paying close attention to widely, has boundless application prospect in fields such as power type electric automobile, portable electric appts.But also there is following shortcoming in lithium-rich manganese-based ternary material: (1) irreversible capacity loss is large first, coulomb efficiency is low; (2) in cyclic process, analyse oxygen, cause safety problem; (3) due to Li 2mnO 3component conductivity is low, causes high rate performance poor; (4) in cyclic process, there is spinelle phase transformation, the reduction of guiding discharge platform and capacitance loss, cyclical stability is poor.
For addressing the above problem, the application adulterates by original position potassium ion, reduces irreversible capacity loss, improve a coulomb efficiency, strengthen high rate performance, especially strengthen its cyclical stability, slowed down the reduction of voltage platform in cyclic process, thereby improve discharge energy density.And the method be suitable for mechanical ball milling production procedure, technique simple, be easy to control, have heavy industrialization application prospect.
Summary of the invention
The application's object is to provide a kind of lithium ion battery original position potassium lithium-rich manganese-based oxide anode material that adulterates, and the chemical formula of this positive electrode can be expressed as: Li (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2, wherein 0.3≤x≤0.9, y=(1+x)/162.
Described positive electrode has a-NaFeO 2type stratiform rock salt structure, belongs to hexagonal crystal system, and space group is R-3m; Wherein, lithium ion and potassium ion occupy the 3a position in structure cell, and nickel, cobalt and manganese ion occupy 3b position, and oxonium ion occupies 6c position.
Described positive electrode, as the positive electrode of lithium ion battery, has high specific discharge capacity, the high rate performance of excellence and stable cyclical stability.
The application's another object is to provide described Li (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2the preparation method of positive electrode, is characterized in that, at least comprises the following steps:
(1) by manganese predecessor, cobalt source, the He Li source, nickel source of potassium doping, mix according to a certain percentage, obtaining having mole proportioning is Mn:Co:Ni:Li=(1+x): (1-x): (1-x): mixture (3+x-3y), wherein 0.3≤x≤0.9, y=(1+x)/162;
(2) mixture of step (1) gained is heat-treated with cold treatment after, obtain the described potassium lithium-rich manganese-based oxide anode material that adulterates.
Preferably, the manganese predecessor of the doping of potassium described in step (1) is obtained through hydrothermal treatment consists by the mixture of potassium permanganate, manganese salt and the concentrated sulfuric acid.According to general knowledge known in this field, Organic Manganese salt and/or inorganic manganese salt all can be used as described manganese salt use arbitrarily.Preferably, described manganese salt is inorganic manganese salt; Further preferably, optionally one or more in manganese acetate, manganese nitrate, manganese chloride, manganese sulfate of described manganese salt.
According to general knowledge known in this field, described in step (1), cobalt source is the arbitrary substance that contains cobalt element, optional one or more in the compound that contains cobalt element; Preferably, optionally one or more in cobalt acetate, cobalt nitrate, cobalt chloride of cobalt source described in step (1).
According to general knowledge known in this field, described in step (1), nickel source is the arbitrary substance that contains nickel element, optional one or more in the compound that contains nickel element; Preferably, optionally one or more in nickel acetate, nickel nitrate, nickel chloride of nickel source described in step (1).
According to general knowledge known in this field, described in step (1), lithium source is the arbitrary substance that contains elemental lithium, optional one or more in the compound that contains elemental lithium; Preferably, optionally one or more in lithium acetate, lithium nitrate, lithium chloride, lithium hydroxide of lithium source described in step (1).
Those skilled in the art can be according to the needs of actual production and cost, selects suitable cobalt source, He Li source, nickel source.
The optional self-grind hybrid mode of mode and/or mixed solution-evaporation hybrid mode of preferably, described in step (1), mixing.For the technical scheme that relates to ground and mixed mode, both can adopt manual mortar to grind, also can adopt mechanical lapping.While adopting mechanical lapping hybrid mode, preferred mechanical ball milling hybrid mode.According to the common practise of this area, described mixed solution-evaporation hybrid mode is, will contain the mixed solution of several raw materials, obtains the hybrid mode of solid mixture after evaporating solvent.Those skilled in the art can, according to the specific requirement in actual production, select suitable hybrid mode.
Preferably, heat treated temperature described in step (2) is 800 DEG C～1000 DEG C, heat treated time 3～16h.
Preferably, one or more in optionally cooling in cooling in cooling under room temperature, liquid nitrogen, mixture of ice and water of the mode of cooling processing described in step (2).
As one preferred embodiment, the preparation method of described positive electrode, at least comprises the steps:
(a) prepare the manganese predecessor of potassium doping: by potassium permanganate, manganese salt and concentrated sulfuric acid dissolution in deionized water, homogeneous phase mixed liquor stirs to obtain, be transferred in water heating kettle, keep a period of time to carry out after hydrothermal treatment consists in uniform temperature, through cooling, filtering and washing, dry, grind after, obtain the manganese predecessor of described potassium doping;
(b) by manganese predecessor, cobalt source, the He Li source, nickel source of the doping of step (a) gained potassium, mix according to a certain percentage, obtaining having mole proportioning is Mn:Co:Ni:Li=(1+x): (1-x): (1-x): mixture (3+x-3y), wherein 0.3≤x≤0.9, y=(1+x)/162;
(c) by step (b) obtain mixture heat-treat with cold treatment after, obtain described positive electrode Li (3+x)/3-yk ymn ( 1+x)/3co (1-x)/3ni (1-x)/3o 2.
Preferably, in described step (a), the ratio of the potassium permanganate of homogeneous phase mixed liquor, manganese salt, sulfuric acid molar concentration is potassium permanganate: manganese salt: sulfuric acid=1～5:3～7:7～13; Further preferably, the ratio of the potassium permanganate in described step (a), manganese salt, sulfuric acid molar concentration is potassium permanganate: manganese salt: sulfuric acid=2～4:4～6:9～11.Optionally one or more in manganese acetate, manganese nitrate, manganese chloride, manganese sulfate of described manganese salt.Preferably, in described step (a), the temperature of hydrothermal treatment consists is 100～200 DEG C, and the processing time is 10～60min.
The application's another object is to provide a kind of lithium ion battery, it is characterized in that: in the positive pole of described lithium ion battery, contain described positive electrode Li (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2and/or the positive electrode preparing according to aforementioned either method.
Described in the application, the beneficial effect of technical scheme is:
Li prepared by the application (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2positive electrode, the reduction with voltage platform in high specific discharge capacity, excellent high rate performance and stable circulation ability, especially cyclic process has obtained effective inhibition, and the loss of energy density is eased.In addition, the method that the application takes, has shortened processing step greatly, has saved ample resources, contributes to sequencing to produce, and has saved production cost.The raw material sources that the application adopts are extensive, and process engineering is simple, are easy to control, reproducible, can scale synthesize.The synthetic method that the application adopts is not limited to the material that the application announces, and can also be used for the synthetic of other materials, and the method has broad application prospects.
Should be understood that within the scope of the technical scheme disclosing in the application, above-mentioned each technical characterictic of the application and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tire out and state no longer one by one at this.
Unless otherwise defined, the familiar meaning of all specialties that use in literary composition and scientific words and one skilled in the art is identical.In addition, any method similar or impartial to described content and material all can be applicable in the application's method, the use that the better implementation method described in literary composition and material only present a demonstration.
Brief description of the drawings
Fig. 1 is the X-ray diffracting spectrum of sample 1#.
Fig. 2 is the scanning electron microscope (SEM) photograph of sample 1#.
Fig. 3 is that sample 1# is as at room temperature 20mAg of positive pole -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1time charging and discharging curve.
Fig. 4 is that sample 1# is as at room temperature 20mAg of positive pole -1, 400mAg -1time cycle performance curve.
Embodiment
The above-mentioned feature that the application mentions, or the feature that embodiment mentions can combination in any.All features that this case specification discloses can with any composition forms use, each feature disclosing in specification, can be replaced by any alternative characteristics that identical, impartial or similar object are provided.Therefore apart from special instruction, the feature disclosing is only the general example of equalization or similar features.
Do not do in the situation of specified otherwise, raw material that the application uses, all buys by commercial sources, directly uses without special processing.
The application's main implementation process is:
(1) first prepare the manganese predecessor that potassium adulterates: take a certain amount of potassium permanganate, manganese salt and concentrated sulfuric acid dissolution in deionized water, stir 10min and form homogeneous phase solution, then be transferred in water heating kettle, be warming up to uniform temperature, keep this temperature some minutes, after cooling, carry out suction filtration, with deionized water by washing of precipitate repeatedly to remove surface impurity ion, gained is deposited in to air drying, after grinding, saves backup.
(2) take manganese predecessor, cobalt salt, nickel salt and the lithium salts of the potassium doping that step (1) obtains, the ratio that makes metal ions M n:Co:Ni:Li is (1+x)/3:(1-x)/3:(1-x)/3:(3+x)/3-y, wherein 0.3≤x≤0.9, y=(1+x)/162, mixes by certain way.
(3) by step (2) obtain mixture heat-treat with cold treatment after, obtain Li (3+x)/3-yk ymn ( 1+x)/3co (1-x)/3ni (1-x)/3o 2.
Below in conjunction with embodiment, further set forth the application.Should be understood that these embodiment are only not used in restriction the application's scope for the application is described.The experimental technique of unreceipted actual conditions in the following example, the condition of conventionally advising according to normal condition or according to manufacturer.
Further illustrate below the application's feature by example, but be not limited to embodiment.
If no special instructions, in embodiment, the test condition to sample is as follows:
X-ray powder diffraction material phase analysis (XRD) carries out on Rigaku Miniflex type X-ray diffractometer, Cu target, K α radiation source (λ=0.15418nm).
Scanning electron microscope sem morphology analysis carries out in JSM 6700 type scanning electron microscopy.
Embodiment 1:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, 0.474g potassium permanganate, 0.845g manganese sulfate, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, transfer them in reactor, be warming up to 150 DEG C of insulation 20min, suction filtration after cooling, is dried afterwards for 3 times and obtains the manganese predecessor that potassium adulterates with deionized water washing; By after gained predecessor 0.55g and 0.4430g nickel nitrate, 0.4440g cobalt nitrate and the abundant ground and mixed of 0.5909g lithium hydroxide, pack crucible into; In box type furnace, be warmed up at 900 DEG C and heat 12h with the programming rate of 2 DEG C/min, and cooling under room temperature, the positive electrode Li can obtain x=0.62 time (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2, wherein y=(1+x)/162, is designated as sample 1#.
The XRD test result demonstration of sample 1#, synthetic powder has stratiform rock salt structure (R-3m), as shown in Figure 1.
The SEM test result of sample 1# as shown in Figure 2, even particle distribution, particle size is 300～500nm.
Sample 1# is as at room temperature 20mAg of positive pole -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1time charging and discharging curve as shown in Figure 3.Adopt button cell to test, the mass ratio of sample 1#, conductive carbon black and binding agent PVdF (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL -1liPF 6/ EC+DMC+EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARE TC53, and charging/discharging voltage window is 2.0～4.8V, and charging and discharging currents density is chosen respectively 20mAg -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1.This material shows good chemical property during as lithium ion battery anodal.Button cell test result shows, is 20mAg in current density -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1under charging and discharging currents density and 28 DEG C at first discharge specific capacity be respectively 315.4mAhg -1, 253.6mAhg -1, 223.3mAhg -1, 214.5mAhg -1, 200.7mAhg -1; After discharging and recharging through 110 times, be 20mAg in current density -1and 400mAg -1time, their specific discharge capacity is respectively 267.0mA h g -1, 175.0mA h g -1, as shown in Figure 4.
Embodiment 2:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, 0.474g potassium permanganate, 0.845g manganese sulfate, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, transfer them in reactor, be warming up to 160 DEG C of insulation 30min, suction filtration after cooling, is dried afterwards for 3 times and obtains the manganese predecessor that potassium adulterates with deionized water washing; By after gained predecessor 0.55g and 0.9905g nickel nitrate, 0.9913g cobalt nitrate and the abundant ground and mixed of 0.6690g lithium hydroxide, pack crucible into; In box type furnace, be warmed up at 850 DEG C and heat 12h with the programming rate of 2 DEG C/min, and cooling in frozen water, the positive electrode Li can obtain x=0.3 time (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2, wherein y=(1+x)/162, is designated as sample 2#.
The XRD test result demonstration of sample 2#, its XRD diffraction maximum position is identical with the XRD diffraction maximum position of sample 1#, and peak intensity is difference slightly, has the stratiform rock salt structure (R-3m) identical with sample 1#.
The SEM test result demonstration of sample 2#, synthetic powder granule is evenly distributed, and particle size is 200～400nm.
Adopt button cell to carry out charge-discharge test to sample 2#, the mass ratio of sample 2#, conductive carbon black and binding agent PVdF (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL -1liPF 6/ EC+DMC+EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARETC53, and charging/discharging voltage window is 2.0～4.8V, and charging and discharging currents density is chosen respectively 20mAg -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1.This material shows good chemical property during as lithium ion battery anodal.Button cell test result shows, is 20mAg in current density -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1under charging and discharging currents density and 28 DEG C at first discharge specific capacity be respectively 305.9mAhg -1, 255.2mAhg -1, 230.3mAhg -1, 224.9mAhg -1, 203.3mAhg -1; After discharging and recharging through 30 times, their specific discharge capacity is respectively 286.9mAhg -1, 239.6mAhg -1, 212.6mAhg -1, 203.9mAhg -1, 178.8mAhg -1.
Embodiment 3:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, 0.474g potassium permanganate, 0.845g manganese sulfate, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, transfer them in reactor, be warming up to 150 DEG C of insulation 20min, suction filtration after cooling, is dried afterwards for 3 times and obtains the manganese predecessor that potassium adulterates with deionized water washing; By after gained predecessor 1.0g and 0.1744g nickel nitrate, 0.1745g cobalt nitrate and the abundant ground and mixed of 0.9820g lithium hydroxide, pack crucible into; In box type furnace, be warmed up at 950 DEG C and heat 12h with the programming rate of 2 DEG C/min, and cooling in liquid nitrogen, the positive electrode Li can obtain x=0.9 time (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2, wherein y=(1+x)/162, is designated as sample 3#.
The XRD test result demonstration of sample 3#, its XRD diffraction maximum position is identical with the XRD diffraction maximum position of sample 1#, and peak intensity is difference slightly, has the stratiform rock salt structure (R-3m) identical with sample 1#.
The SEM test result demonstration of sample 3#, synthetic powder granule is evenly distributed, and particle size is 400～600nm.
Adopt button cell to carry out charge-discharge test to sample 3#, the mass ratio of sample 3#, conductive carbon black and binding agent PVdF (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL -1liPF 6/ EC+DMC+EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARETC53, and charging/discharging voltage window is 2.0～4.8V, and charging and discharging currents density is chosen respectively 20mAg -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1.This material shows good chemical property during as lithium ion battery anodal.Button cell test result shows, is 20mAg in current density -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1under charging and discharging currents density and 28 DEG C at first discharge specific capacity be respectively 290.3mAhg -1, 235.2mAhg -1, 210.6mAhg -1, 202.2mAhg -1, 195.5mAhg -1; After discharging and recharging through 30 times, their specific discharge capacity is respectively 282.1mAhg -1, 230.6mAhg -1, 198.8mAhg -1, 190.2mAhg -1, 184.0mAhg -1.
Embodiment 4:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, 0.474g potassium permanganate, 0.845g manganese sulfate, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, transfer them in reactor, be warming up to 180 DEG C of insulation 20min, suction filtration after cooling, is dried afterwards for 3 times and obtains the manganese predecessor that potassium adulterates with deionized water washing; By after gained predecessor 1.0g and 1.1171 nickel nitrates, 1.1181g cobalt nitrate and the abundant ground and mixed of 1.1178g lithium hydroxide, pack crucible into; In box type furnace, be warmed up at 950 DEG C and heat 12h with the programming rate of 2 DEG C/min, and cooling under room temperature, the positive electrode Li can obtain x=0.5 time (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2, wherein y=(1+x)/162, is designated as sample 4#.
The XRD test result demonstration of sample 4#, its XRD diffraction maximum position is identical with the XRD diffraction maximum position of sample 1#, and peak intensity is difference slightly, has the stratiform rock salt structure (R-3m) identical with sample 1#.
The SEM test result demonstration of sample 4#, synthetic powder granule is evenly distributed, and particle size is 400～600nm.
Adopt button cell to carry out charge-discharge test to sample 4#, the mass ratio of sample 4#, conductive carbon black and binding agent PVdF (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL -1liPF 6/ EC+DMC+EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARETC53, and charging/discharging voltage window is 2.0～4.8V, and charging and discharging currents density is chosen respectively 20mAg -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1.This material shows good chemical property during as lithium ion battery anodal.Button cell test result shows, is 20mAg in current density -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1under charging and discharging currents density and 28 DEG C at first discharge specific capacity be respectively 305.3mAhg -1, 255.3mAhg -1, 231.4mAhg -1, 220.2mAhg -1, 205.7mAhg -1; After discharging and recharging through 30 times, their specific discharge capacity is respectively 285.5mAhg -1, 236.8mAhg -1, 211.1mAhg -1, 204.3mAhg -1, 194.7mAhg -1.
Embodiment 5:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, 0.474g potassium permanganate, 0.845g manganese sulfate, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, transfer them in reactor, be warming up to 150 DEG C of insulation 20min, suction filtration after cooling, is dried afterwards for 3 times and obtains the manganese predecessor that potassium adulterates with deionized water washing; By after gained predecessor 1.0g and 0.3735g nickel nitrate, 0.3738g cobalt nitrate and the abundant ground and mixed of 1.0192g lithium hydroxide, pack crucible into; In box type furnace, be warmed up at 950 DEG C and heat 12h with the programming rate of 2 DEG C/min, and cooling under room temperature, the positive electrode Li can obtain x=0.8 time (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2, wherein y=(1+x)/162, is designated as sample 5#.
The XRD test result demonstration of sample 5#, its XRD diffraction maximum position is identical with the XRD diffraction maximum position of sample 1#, and peak intensity is difference slightly, has the stratiform rock salt structure (R-3m) identical with sample 1#.
The SEM test result demonstration of sample 5#, synthetic powder granule is evenly distributed, and particle size is 400～600nm.
Adopt button cell to carry out charge-discharge test to sample 5#, the mass ratio of sample 5#, conductive carbon black and binding agent PVdF (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL -1liPF 6/ EC+DMC+EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARETC53, and charging/discharging voltage window is 2.0～4.8V, and charging and discharging currents density is chosen respectively 20mAg -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1.This material shows good chemical property during as lithium ion battery anodal.Button cell test result shows, is 20mAg in current density -1, 100mAg -1, 200mAg -1, 400mAg -1, 600mAg -1under charging and discharging currents density and 28 DEG C at first discharge specific capacity be respectively 293.3mAhg -1, 230.1mAhg -1, 206.6mAhg -1, 195.8mAhg -1, 185.5mAhg -1; After discharging and recharging through 30 times, their specific discharge capacity is respectively 279.4mAhg -1, 218.6mAhg -1, 188.8mAhg -1, 181.0mAhg -1, 167.5mAhg -1.
Although the application with preferred embodiment openly as above; but be not for limiting claim; any those skilled in the art are not departing under the prerequisite of the application's design; can make some possible variations and amendment, the scope that therefore the application's protection range should be defined with the application's claim is as the criterion.

Claims (10)

1. the potassium lithium-rich manganese-based oxide anode material that adulterates, is characterized in that: the chemical formula of described positive electrode can be expressed as: Li (3+x)/3-yk ymn (1+x)/3co (1-x)/3ni (1-x)/3o 2, wherein 0.3≤x≤0.9, y=(1+x)/162.
2. a preparation method for positive electrode described in claim 1, is characterized in that, at least comprises the steps:
(1) by manganese predecessor, cobalt source, the He Li source, nickel source of potassium doping, mix according to a certain percentage, obtaining having mole proportioning is Mn:Co:Ni:Li=(1+x): (1-x): (1-x): mixture (3+x-3y), wherein 0.3≤x≤0.9, y=(1+x)/162;
(2) by the mixture of step (1) gained after heat treatment and cold treatment, obtain the described potassium lithium-rich manganese-based oxide anode material that adulterates.
3. preparation method according to claim 2, is characterized in that: the manganese predecessor of the doping of potassium described in step (1) is obtained through hydrothermal treatment consists by the mixture of potassium permanganate, manganese salt and the concentrated sulfuric acid.
4. preparation method according to claim 3, is characterized in that: optionally one or more in manganese acetate, manganese nitrate, manganese chloride, manganese sulfate of described manganese salt.
5. preparation method according to claim 2, is characterized in that: optionally one or more in cobalt acetate, cobalt nitrate, cobalt chloride of cobalt source described in step (1); Optionally one or more in nickel acetate, nickel nitrate, nickel chloride of nickel source described in step (1); Optionally one or more in lithium acetate, lithium nitrate, lithium chloride, lithium hydroxide of lithium source described in step (1).
6. preparation method according to claim 2, is characterized in that: the optional self-grind hybrid mode of mode and/or mixed solution-evaporation hybrid mode of described in step (1), mixing.
7. preparation method according to claim 2, is characterized in that: the mode of mixing described in step (1) is mechanical ball milling hybrid mode.
8. preparation method according to claim 2, is characterized in that: heat treated temperature described in step (2) is 800 DEG C～1000 DEG C, time 3～16h.
9. preparation method according to claim 2, is characterized in that: one or more during the mode of cooling processing described in step (2) is optionally cooling in cooling in cooling under room temperature, liquid nitrogen, mixture of ice and water.
10. a lithium ion battery, is characterized in that: the positive electrode that contains positive electrode claimed in claim 1 in the positive pole of described lithium ion battery and/or prepare according to either method described in right 2-9.
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