CN104091919B - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents

A kind of anode material for lithium-ion batteries and preparation method thereof Download PDF

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CN104091919B
CN104091919B CN201410365645.5A CN201410365645A CN104091919B CN 104091919 B CN104091919 B CN 104091919B CN 201410365645 A CN201410365645 A CN 201410365645A CN 104091919 B CN104091919 B CN 104091919B
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manganese
lithium
potassium
cobalt
nickel
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CN104091919A (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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    • H—ELECTRICITY
    • H01—BASIC 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—BASIC 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—BASIC 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

Abstract

The application discloses lithium-rich manganese-based oxide anode material of a kind of potassium doping and preparation method thereof, and the chemical formula of this positive electrode can be expressed as: Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2, wherein 0.3≤x≤0.9, y=(1+x)/162. This positive electrode has high energy density and excellent cycle performance, high rate performance. Adopt the manganese predecessor of original position potassium doping to be prepared as manganese source, the preparation method's operation adopting has simply, production cost is low, synthesis cycle is short and repeatable advantages of higher, can be widely used in the synthetic of lithium ion battery oxide anode material.

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 that adulteratesAnd preparation method thereof.
Background technology
Lithium-rich manganese-based tertiary cathode material is because its high specific discharge capacity has been subject to paying close attention to widely, at powerThere is boundless application prospect in the fields such as type electric automobile, portable electric appts. But, rich lithium manganeseAlso there is following shortcoming in base 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 Li2MnO3Component electrical conductivity is low, causes multiplying powerPoor performance; (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, improvesCoulomb efficiency, strengthens high rate performance, especially strengthens its cyclical stability, to have slowed down in cyclic process voltage flatThe reduction of platform, thus discharge energy density improved. And the method is suitable for mechanical ball milling production procedure, workSkill is 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 adulteratesMaterial, the chemical formula of this positive electrode can be expressed as: Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2, wherein0.3≤x≤0.9，y＝(1+x)/162。
Described positive electrode has a-NaFeO2Type stratiform rock salt structure, belongs to hexagonal crystal system, and space group isR-3m; Wherein, lithium ion and potassium ion occupy the 3a position in structure cell, and nickel, cobalt and manganese ion occupy 3bPosition, oxonium ion occupies 6c position.
Described positive electrode is as the positive electrode of lithium ion battery, has high specific discharge capacity, excellentHigh rate performance and stable cyclical stability.
The application's another object is to provide described Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2Anodal materialThe preparation method of material, 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, obtainHaving mole proportioning is Mn:Co:Ni:Li=(1+x): (1-x): (1-x): mixture (3+x-3y), wherein0.3≤x≤0.9，y＝(1+x)/162；
(2) mixture of step (1) gained is heat-treated with cold treatment after, obtain the doping of described potassium richLithium manganese-base oxide positive electrode.
Preferably, the manganese predecessor of potassium described in step (1) doping is by potassium permanganate, manganese salt and the concentrated sulfuric acidMixture obtains through hydrothermal treatment consists. According to general knowledge known in this field, Organic Manganese salt and/or inorganic manganese salt are equal arbitrarilyCan be used as described manganese salt uses. Preferably, described manganese salt is inorganic manganese salt; Further preferably, described manganeseSalt is one or more in manganese acetate, manganese nitrate, manganese chloride, manganese sulfate optionally.
According to general knowledge known in this field, described in step (1), cobalt source is the arbitrary substance that contains cobalt element, appointsBe selected from one or more in the compound that contains cobalt element; Preferably, described in step (1), cobalt source is optionalOne or more in cobalt acetate, cobalt nitrate, cobalt chloride.
According to general knowledge known in this field, described in step (1), nickel source is the arbitrary substance that contains nickel element, appointsBe selected from one or more in the compound that contains nickel element; Preferably, described in step (1), nickel source is optionalOne or more in nickel acetate, nickel nitrate, nickel chloride.
According to general knowledge known in this field, described in step (1), lithium source is the arbitrary substance that contains elemental lithium, appointsBe selected from one or more in the compound that contains elemental lithium; Preferably, described in step (1), lithium source is optionalOne or more in lithium acetate, lithium nitrate, lithium chloride, lithium hydroxide.
Those skilled in the art can be according to the needs of actual production and cost, select suitable cobalt source, nickel source andLithium source.
The optional self-grind hybrid mode of mode of preferably, mixing described in step (1) and/or mixed solution-Evaporation hybrid mode. 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 toThe common practise of this area, described mixed solution-evaporation hybrid mode is, by molten the mixing that contains several raw materialsLiquid, obtains the hybrid mode of solid mixture after evaporating solvent. Those skilled in the art can be according to actual productionIn specific requirement, select suitable hybrid mode.
Preferably, heat treated temperature described in step (2) is 800 DEG C～1000 DEG C, the heat treated time 3～16h。
Preferably, the mode of cooling processing described in step (2) optionally cooling in cooling under room temperature, liquid nitrogen,One or more in cooling in mixture of ice and water.
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 waterIn, the homogeneous phase mixed liquor that stirs to obtain, is transferred in water heating kettle, keeps a period of time to carry out in uniform temperatureAfter hydrothermal treatment consists, 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, according to certain ratioExample is mixed, and obtaining having mole proportioning is Mn:Co:Ni:Li=(1+x): (1-x): (1-x): (3+x-3y) mixedCompound, 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 electrodeLi(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2。
Preferably, the potassium permanganate of homogeneous phase mixed liquor in described step (a), manganese salt, sulfuric acid molar concentrationRatio is potassium permanganate: manganese salt: sulfuric acid=1～5:3～7:7～13; Further preferably, described step (a)In potassium permanganate, manganese salt, the ratio of sulfuric acid molar concentration be 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. ExcellentSelection of land, in described step (a), the temperature of hydrothermal treatment consists is 100～200 DEG C, 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: described lithium ion batteryPositive pole in contain described positive electrode Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2And/or according to aforementionedThe positive electrode that either method prepares.
Described in the application, the beneficial effect of technical scheme is:
Li prepared by the application(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2Positive electrode, has high electric dischargeIn the high rate performance of specific capacity, excellence and stable circulation ability, especially cyclic process, voltage platform fallsLowly obtained effective inhibition, the loss of energy density is eased. In addition, the method that the application takes,Shorten greatly processing step, saved ample resources, contributed to sequencing to produce, saved and be produced intoThis. The raw material sources that the application adopts are extensive, and process engineering is simple, are easy to control, reproducible, canScale is synthetic. The synthetic method that the application adopts is not limited to the material that the application announces, and can also be used forSynthesizing of other materials, the method has broad application prospects.
Should be understood that the application disclose technical scheme within the scope of, above-mentioned each technical characterictic of the application and underIn literary composition (as embodiment), can combine mutually between specifically described each technical characterictic, thus form new orPreferred technical scheme. As space is limited, tire out and state no longer one by one at this.
Unless otherwise defined, all specialties that use in literary composition and scientific words and one skilled in the art are familiar withMeaning identical. In addition, any method similar or impartial to described content and material all can be applicable to thisIn application 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、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1Time charging and discharging curve.
Fig. 4 is that sample 1# is as at room temperature 20mAg of positive pole-1、400mA·g-1Time cycle performance curve.
Detailed description of the invention
The above-mentioned feature that the application mentions, or the feature that embodiment mentions can be combined. This case description instituteDisclose all features can with any composition forms use, each feature disclosing in description, canProvided alternative characteristics identical, impartial or similar object to replace by any. Therefore apart from special instruction, instituteThe 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, without spyDifferent processing directly used.
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 the concentrated sulfuric acidBe dissolved in deionized water, stir 10min and form homogeneous phase solution, be then transferred in water heating kettle, heat upTo uniform temperature, keep this temperature some minutes, after cooling, carry out suction filtration, by deionized water by washing of precipitateRepeatedly, 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, make metalThe ratio of ion Mn: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, obtainLi(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2。
Below in conjunction with embodiment, further set forth the application. Should be understood that these embodiment are only for illustrating this ShenPlease and be not used in restriction the application scope. The experimental technique of unreceipted actual conditions in the following example is logicalNormal condition of 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 RigakuMiniflex type X-ray diffractometer,Cu target, K α radiation source (λ=0.15418nm).
Scanning electron microscope sem morphology analysis carries out in JSM6700 type SEM.
Embodiment 1:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, by 0.474g potassium permanganate, 0.845g sulphurAcid manganese, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, by itBe transferred in reactor, be warming up to 150 DEG C of insulation 20min, suction filtration after cooling, with deionized water washing 3The inferior rear dry manganese predecessor that obtains potassium doping; By gained predecessor 0.55g and 0.4430g nickel nitrate,After 0.4440g cobalt nitrate and the abundant ground and mixed of 0.5909g lithium hydroxide, pack crucible into; In batch-type furnaceBe warmed up at 900 DEG C and heat 12h with the programming rate of 2 DEG C/min, and cooling under room temperature, can obtainPositive electrode Li when x=0.62(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2, wherein y=(1+x)/162, noteFor sample 1#.
The XRD test result demonstration of sample 1#, synthetic powder has stratiform rock salt structure (R-3m), as figureShown in 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、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1Time charging and discharging curve as shown in Figure 3. Adopt button cell to test, sample 1#, leadBlack and mass ratio binding agent PVdF (Kynoar) of electrical carbon is 8:1:1, and metal lithium sheet is to electrode,1mol·L-1LiPF6/ EC+DMC+EMC (volume ratio 1:1:1) is electrolyte, polypropylene material be everyFilm, battery test system is NEWARETC53, charging/discharging voltage window is 2.0～4.8V, discharges and recharges electricityCurrent density is chosen respectively 20mAg-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1。This material shows good chemical property during as lithium ion battery anodal. Button cell test resultShowing, is 20mAg in current density-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1Under charging and discharging currents density and 28 DEG C at first discharge specific capacity be respectively 315.4mAhg-1、253.6mAh·g-1、223.3mAh·g-1、214.5mAh·g-1、200.7mAh·g-1; Discharge and recharge it through 110 timesAfter, be 20mAg in current density-1And 400mAg-1Time, their specific discharge capacity is respectively 267.0mAhg-1、175.0mAhg-1, as shown in Figure 4.
Embodiment 2:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, by 0.474g potassium permanganate, 0.845g sulphurAcid manganese, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, by itBe transferred in reactor, be warming up to 160 DEG C of insulation 30min, suction filtration after cooling, with deionized water washing 3The inferior rear dry manganese predecessor that obtains potassium doping; By gained predecessor 0.55g and 0.9905g nickel nitrate,After 0.9913g cobalt nitrate and the abundant ground and mixed of 0.6690g lithium hydroxide, pack crucible into; In batch-type furnace withThe programming rate of 2 DEG C/min is warmed up at 850 DEG C and heats 12h, and cooling in frozen water, can obtain x=0.3Time positive electrode Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2, wherein y=(1+x)/162, is designated as sample2#。
The XRD test result of sample 2# shows, the XRD diffraction of its XRD diffraction maximum position and sample 1Peak position is identical, 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 is200～400nm。
Adopt button cell sample 2# to be carried out to charge-discharge test, sample 2#, conductive carbon black and binding agent PVdFThe mass ratio of (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL-1LiPF6/EC+DMC+ EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARETC53, charging/discharging voltage window is 2.0～4.8V, charging and discharging currents density is chosen respectively 20mAg-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1. This material is as the positive pole of lithium ion batteryTime show good chemical property. Button cell test result shows, is 20mAg in current density-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1Under charging and discharging currents density and 28 DEG CLower first discharge specific capacity is respectively 305.9mAhg-1、255.2mAh·g-1、230.3mAh·g-1、224.9mAh·g-1、203.3mAh·g-1; After discharging and recharging through 30 times, their specific discharge capacity is respectively 286.9mAh·g-1、239.6mAh·g-1、212.6mAh·g-1、203.9mAh·g-1、178.8mAh·g-1。
Embodiment 3:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, by 0.474g potassium permanganate, 0.845g sulphurAcid manganese, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, by itBe transferred in reactor, be warming up to 150 DEG C of insulation 20min, suction filtration after cooling, with deionized water washing 3The inferior rear dry manganese predecessor that obtains potassium doping; By gained predecessor 1.0g and 0.1744g nickel nitrate,After 0.1745g cobalt nitrate and the abundant ground and mixed of 0.9820g lithium hydroxide, pack crucible into; In batch-type furnace withThe programming rate of 2 DEG C/min is warmed up at 950 DEG C and heats 12h, and cooling in liquid nitrogen, can obtain x=0.9Time positive electrode Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2, wherein y=(1+x)/162, is designated as sample3#。
The XRD test result of sample 3# shows, the XRD diffraction of its XRD diffraction maximum position and sample 1Peak position is identical, 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 is400～600nm。
Adopt button cell sample 3# to be carried out to charge-discharge test, sample 3#, conductive carbon black and binding agent PVdFThe mass ratio of (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL-1LiPF6/EC+DMC+ EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARETC53, charging/discharging voltage window is 2.0～4.8V, charging and discharging currents density is chosen respectively 20mAg-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1. This material is as the positive pole of lithium ion batteryTime show good chemical property. Button cell test result shows, is 20mAg in current density-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1Under charging and discharging currents density and 28 DEG CLower first discharge specific capacity is respectively 290.3mAhg-1、235.2mAh·g-1、210.6mAh·g-1、202.2mAh·g-1、195.5mAh·g-1; After discharging and recharging through 30 times, their specific discharge capacity is respectively 282.1mAh·g-1、230.6mAh·g-1、198.8mAh·g-1、190.2mAh·g-1、184.0mAh·g-1。
Embodiment 4:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, by 0.474g potassium permanganate, 0.845g sulphurAcid manganese, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, by itBe transferred in reactor, be warming up to 180 DEG C of insulation 20min, suction filtration after cooling, with deionized water washing 3The inferior rear dry manganese predecessor that obtains potassium doping; By gained predecessor 1.0g and 1.1171 nickel nitrates, 1.1181gAfter cobalt nitrate and the abundant ground and mixed of 1.1178g lithium hydroxide, pack crucible into; In batch-type furnace with 2 DEG C/minProgramming rate be warmed up at 950 DEG C and heat 12h, and cooling under room temperature, can obtain x=0.5 time justUtmost point material Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2, wherein y=(1+x)/162, is designated as sample 4#.
The XRD test result of sample 4# shows, the XRD diffraction of its XRD diffraction maximum position and sample 1Peak position is identical, 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 is400～600nm。
Adopt button cell sample 4# to be carried out to charge-discharge test, sample 4#, conductive carbon black and binding agent PVdFThe mass ratio of (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL-1LiPF6/EC+DMC+ EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARETC53, charging/discharging voltage window is 2.0～4.8V, charging and discharging currents density is chosen respectively 20mAg-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1. This material is as the positive pole of lithium ion batteryTime show good chemical property. Button cell test result shows, is 20mAg in current density-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1Under charging and discharging currents density and 28 DEG CLower first discharge specific capacity is respectively 305.3mAhg-1、255.3mAh·g-1、231.4mAh·g-1、220.2mAh·g-1、205.7mAh·g-1; After discharging and recharging through 30 times, their specific discharge capacity is respectively 285.5mAh·g-1、236.8mAh·g-1、211.1mAh·g-1、204.3mAh·g-1、194.7mAh·g-1。
Embodiment 5:
Taking potassium permanganate, manganese sulfate, the concentrated sulfuric acid as initiation material, by 0.474g potassium permanganate, 0.845g sulphurAcid manganese, the 1mL concentrated sulfuric acid are dissolved in 15mL deionized water, stir 10min and form homogeneous phase solution, by itBe transferred in reactor, be warming up to 150 DEG C of insulation 20min, suction filtration after cooling, with deionized water washing 3The inferior rear dry manganese predecessor that obtains potassium doping; By gained predecessor 1.0g and 0.3735g nickel nitrate,After 0.3738g cobalt nitrate and the abundant ground and mixed of 1.0192g lithium hydroxide, pack crucible into; In batch-type furnace withThe programming rate of 2 DEG C/min is warmed up at 950 DEG C and heats 12h, and cooling under room temperature, can obtain x=0.8Time positive electrode Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2, wherein y=(1+x)/162, is designated as sample5#。
The XRD test result of sample 5# shows, the XRD diffraction of its XRD diffraction maximum position and sample 1Peak position is identical, 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 is400～600nm。
Adopt button cell sample 5# to be carried out to charge-discharge test, sample 5#, conductive carbon black and binding agent PVdFThe mass ratio of (Kynoar) is 8:1:1, and metal lithium sheet is to electrode, 1molL-1LiPF6/EC+DMC+ EMC (volume ratio 1:1:1) is electrolyte, and polypropylene material is barrier film, and battery test system is NEWARETC53, charging/discharging voltage window is 2.0～4.8V, charging and discharging currents density is chosen respectively 20mAg-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1. This material is as the positive pole of lithium ion batteryTime show good chemical property. Button cell test result shows, is 20mAg in current density-1、100mA·g-1、200mA·g-1、400mA·g-1、600mA·g-1Under charging and discharging currents density and 28 DEG CLower first discharge specific capacity is respectively 293.3mAhg-1、230.1mAh·g-1、206.6mAh·g-1、195.8mAh·g-1、185.5mAh·g-1; After discharging and recharging through 30 times, their specific discharge capacity is respectively 279.4 mAh·g-1、218.6mAh·g-1、188.8mAh·g-1、181.0mAh·g-1、167.5mAh·g-1。
Although the application with preferred embodiment openly as above, is not for limiting claim, any abilityField technique personnel, not departing under the prerequisite of the application's design, can make some possible variations and amendment,Therefore the scope that the application's protection domain 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 change of described positive electrodeFormula can be expressed as: Li(3+x)/3-yKyMn(1+x)/3Co(1-x)/3Ni(1-x)/3O2, wherein 0.3≤x≤0.9, y=(1+x)/162；
Described positive electrode has a-NaFeO2Type stratiform rock salt structure, belongs to hexagonal crystal system, and space group isR-3m。
2. a preparation method for positive electrode described in claim 1, is characterized in that, at least comprises followingStep:
(1) by manganese predecessor, cobalt source, the He Li source, nickel source of potassium doping, mix according to a certain percentage, obtainHaving mole proportioning is Mn:Co:Ni:Li=(1+x): (1-x): (1-x): mixture (3+x-3y), wherein0.3≤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 rich lithium that adulteratesManganese-base oxide positive electrode.
3. preparation method according to claim 2, is characterized in that: the doping of potassium described in step (1)Manganese predecessor 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: described manganese salt optionally from manganese acetate,One or more in manganese nitrate, manganese chloride, manganese sulfate.
5. preparation method according to claim 2, is characterized in that: described in step (1), appoint in cobalt sourceBe selected from one or more in cobalt acetate, cobalt nitrate, cobalt chloride; Described in step (1), nickel source is optionally from secondOne or more in acid nickel, nickel nitrate, nickel chloride; Lithium source described in step (1) optionally from lithium acetate,One or more in lithium nitrate, lithium chloride, lithium hydroxide.
6. preparation method according to claim 2, is characterized in that: described in step (1), mixThe optional self-grind hybrid mode of mode and/or mixed solution-evaporation hybrid mode.
7. preparation method according to claim 2, is characterized in that: described in step (1), mixMode is mechanical ball milling hybrid mode.
8. preparation method according to claim 2, is characterized in that: heat treatment described in step (2)Temperature be 800 DEG C～1000 DEG C, time 3～16h.
9. preparation method according to claim 2, is characterized in that: cooling place described in step (2)One or more during the mode of reason 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: in the positive pole of described lithium ion battery, contain claimPositive electrode described in 1 and/or the positive electrode preparing according to either method described in right 2-9.
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