CN109411733A - Modified anode material for lithium-ion batteries of compound coating and preparation method thereof, anode and lithium ion battery - Google Patents

Modified anode material for lithium-ion batteries of compound coating and preparation method thereof, anode and lithium ion battery Download PDF

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Publication number
CN109411733A
CN109411733A CN201811314411.2A CN201811314411A CN109411733A CN 109411733 A CN109411733 A CN 109411733A CN 201811314411 A CN201811314411 A CN 201811314411A CN 109411733 A CN109411733 A CN 109411733A
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nano
oxide
metal
lithium
roasting
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Inventor
程洁
陈玉超
张伟
周舟
刘玉玺
王丽萍
陈社
张敏
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Yantai Zhuoneng Lithium Battery Co Ltd
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Yantai Zhuoneng Lithium Battery Co Ltd
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Priority to CN201811314411.2A priority Critical patent/CN109411733A/en
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

This disclosure relates to the anode material for lithium-ion batteries and preparation method thereof that a kind of compound coating is modified, anode and lithium ion battery, the positive electrode includes composite material of core-shell structure, composite material of core-shell structure includes kernel and the shell for being coated on core surface, kernel is nickle cobalt lithium manganate particle, shell includes the first nano-metal-oxide and the second nano-metal-oxide, first nano-metal-oxide is nanometer tungsten oxide, second nano-metal-oxide includes nano aluminium oxide, nano silicon oxide, nano-titanium oxide, at least one of nano zircite and nano magnesia, with elemental metal, the weight ratio of first nano-metal-oxide and the second nano-metal-oxide is 1:(0.5~2.0).The positive electrode contains the composite material of core-shell structure of stable structure, and structure collapses are not susceptible in ion deinsertion, and specific capacity is higher, cycle performance and good rate capability；It can be reduced electrolyte to contact with the direct of kernel, reduce side reaction, promote the security performance of electrode material.

Description

Modified anode material for lithium-ion batteries of compound coating and preparation method thereof, anode and Lithium ion battery
Technical field
This disclosure relates to field of lithium ion battery, and in particular, to a kind of lithium ion cell positive that compound coating is modified Material and preparation method thereof, anode and lithium ion battery.
Background technique
Life, environment, the energy are the three big global problems that the mankind face in 21 century, especially global shortage of resources It becomes increasingly conspicuous, the development of new energy is particularly important.In recent years, new-energy automobile relies on its energy-saving and emission-reduction, convenient environment friendly Great attention of the advantage by national governments.New-energy automobile is using lithium-ion-power cell as dynamical system, positive material Expect the key component as lithium-ion-power cell, the superiority and inferiority of performance directly affects service life and the security performance of power battery.
Traditional lithium-ion-power cell mainly uses the LiFePO4 of olivine structural, but the energy of LiFePO4 is close It spends low, limits its large-scale application in electric passenger vehicle.
Nickelic tertiary cathode material is α-NaFeO2Layer structure, practical reversible specific capacity can achieve 200mAh/g or Person is higher, and mass energy density and volume energy density are with the obvious advantage, multiplies suitable for more demanding electronic of course continuation mileage With vehicle power battery.But with the raising of nickel content, during the ion deinsertion of nickel-cobalt lithium manganate material lithium under high voltages It easily undergoes phase transition and leads to structure collapses, cause battery capacity decaying and cycle performance declines.In addition, nickelic ternary material is filling Quick capacity attenuation and impedance rise are shown in discharge process, the crystal and electronics on material particles surface when especially charging Structure is uneven, and the abjection amount of particle surface Li is bigger, causes material structure unstable.Nickelic tertiary cathode material is come It says, the unstable of material structure is the root unfavorable to battery system, seriously affects the cycle performance and security performance of material.
Summary of the invention
Purpose of this disclosure is to provide a kind of anode material for lithium-ion batteries, to improve the circulation of nickelic tertiary cathode material Performance, high rate performance and security performance.
Disclosure first aspect provides a kind of anode material for lithium-ion batteries, which includes core-shell structure composite wood Material, the composite material of core-shell structure include kernel and the shell for being coated on the core surface, and the kernel is nickel cobalt mangaic acid Lithium particle, the shell include the first nano-metal-oxide and the second nano-metal-oxide, the first nano metal oxygen Compound is nanometer tungsten oxide, second nano-metal-oxide include nano aluminium oxide, nano silicon oxide, nano-titanium oxide, At least one of nano zircite and nano magnesia, with elemental metal, first nano-metal-oxide and described The weight ratio of second nano-metal-oxide is 1:(0.5~2.0).
Optionally, the average grain diameter of the composite material of core-shell structure is 8~14 μm.
Optionally, the kernel is the second particle of nickle cobalt lithium manganate, and the chemical formula of the nickle cobalt lithium manganate is Li (NixCoyMn1-x-y)O2, wherein 0.6≤x≤0.9,0.05≤y≤0.2.
Optionally, the peak intensity I of (003) diffraction maximum of the XRD spectra of the composite material of core-shell structure003(104) spread out Penetrate the peak intensity I at peak104Ratio I003/I104For 1.1≤I003/I104≤1.5；Spread out (104) of the composite material of core-shell structure The half-peak breadth for penetrating peak is 0.2~0.26.
Optionally, the nickle cobalt lithium manganate particle and first nano-metal-oxide and the second nano metal oxygen The weight ratio of compound is 1:(0.0005~0.005): (0.00025~0.0025).
Optionally, second nano-metal-oxide is the mixture of nano-titanium oxide and nano aluminium oxide；With metal Element meter, the weight ratio of the nanometer tungsten oxide, the nano-titanium oxide and the nano aluminium oxide be 1:(0.25~ 1.0): (0.25~1.0).
Disclosure second aspect provides the method for anode material for lithium-ion batteries described in preparation disclosure first aspect, should Method includes the following steps: S1, after mixing nickel-cobalt-manganese ternary presoma with lithium source progress first, then in oxygen-containing gas atmosphere The first roasting is carried out, the temperature of first roasting is 800~950 DEG C, and the time is 10~20h, obtains the first product of roasting； S2 makes first product of roasting and first nano-metal-oxide and second nano-metal-oxide carry out second The second roasting is carried out after mixing, the temperature of second roasting is 400~600 DEG C, and the time is 8~16h, obtains the lithium ion Cell positive material；In terms of elemental lithium the dosage molar ratio of the lithium source and the nickel-cobalt-manganese ternary presoma be (1.010~ 1.060): 1, with the first nano-metal-oxide described in elemental metal, second nano-metal-oxide and described first The dosage weight ratio of product of roasting is (0.0005~0.005): (0.00025~0.0025): 1.
Optionally, the oxygen content of the oxygen-containing gas atmosphere is 50~100mol%；First nano metal oxide The partial size of object is 10~100nm, and the partial size of second nano-metal-oxide is 10~100nm；The lithium source is selected from carbon Sour lithium, lithium hydroxide, lithium acetate or lithium fluoride, or be the two or three in them or four combination；The nickel cobalt manganese three The structural formula of first presoma is NixCoyMn1-x-y(OH)2, wherein 0.6≤x≤0.9,0.05≤y≤0.2.
Optionally, first nano-metal-oxide is nanometer tungsten oxide, and second nano-metal-oxide is to receive The mixture of rice titanium oxide and nano aluminium oxide；With nanometer tungsten oxide described in elemental metal, the nano-titanium oxide and described The weight ratio of nano aluminium oxide is 1:(0.25~1.0): (0.25~1.0)；The nanometer tungsten oxide, the nano-titanium oxide It is 1:(0.2~1.0 with the ratio between the partial size of the nano aluminium oxide): (0.2~1.0).
Optionally, this method further include: before step S2, step that first product of roasting is crushed, sieved Suddenly；The partial size of the first product of roasting after the crushing, screening is 8~14 μm；The material that second roasting obtains is carried out It crushes, screening, obtains the anode material for lithium-ion batteries.
The disclosure third aspect provides a kind of lithium ion cell positive, which includes lithium described in disclosure first aspect Ion battery positive electrode.
Disclosure fourth aspect provides a kind of lithium ion battery, which includes lithium ion described in the disclosure third aspect Anode.
Through the above technical solutions, the disclosure is by containing the nano metal of tungsten oxide in nickle cobalt lithium manganate kernel outer cladding Oxide shells obtain the composite material of core-shell structure, and the grain structure of the composite material of core-shell structure is stablized, in ion deinsertion It is not susceptible to structure collapses in the process, thus the anode material for lithium-ion batteries containing the composite material of core-shell structure can either be tieed up The higher specific capacity of nickel-cobalt lithium manganate material is held, and there is preferable cycle performance and high rate performance；The core-shell structure is multiple simultaneously Condensation material can reduce electrolyte and contact with the direct of positive electrode kernel, the generation of side reaction be reduced, to improve electrode The security performance of material.The cladding process of disclosed method is simple and easy, and production cost is low, is suitable for being mass produced.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:
Fig. 1 is the XRD spectra of composite material of core-shell structure prepared by embodiment 1；
Fig. 2 is the transmission electron microscope photo of composite material of core-shell structure prepared by embodiment 4；
Fig. 3 is 100 weeks cyclic curves of room temperature 1C@of the positive electrode of embodiment 3；
Fig. 4 is 100 weeks cyclic curves of room temperature 1C@of the positive electrode of comparative example 1；
Specific embodiment
It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
Disclosure first aspect provides a kind of anode material for lithium-ion batteries, which includes core-shell structure composite wood Material, the composite material of core-shell structure include kernel and the shell for being coated on the core surface, and the kernel is nickel cobalt mangaic acid Lithium particle, the shell include the first nano-metal-oxide and the second nano-metal-oxide, the first nano metal oxygen Compound is nanometer tungsten oxide, second nano-metal-oxide include nano aluminium oxide, nano silicon oxide, nano-titanium oxide, At least one of nano zircite and nano magnesia, with elemental metal, first nano-metal-oxide and described The weight ratio of second nano-metal-oxide is 1:(0.5~2.0).
The disclosure obtains core by the nano-metal-oxide shell for containing tungsten oxide in nickle cobalt lithium manganate kernel outer cladding The grain structure of the composite material of shell structure, the composite material of core-shell structure is stablized, and is not susceptible to tie during ion deinsertion Structure collapses, thus the anode material for lithium-ion batteries containing the composite material of core-shell structure can either maintain nickel-cobalt lithium manganate material Higher specific capacity, and there is preferable cycle performance and high rate performance；The composite material of core-shell structure can reduce electricity simultaneously Solution liquid is directly contacted with positive electrode kernel, the generation of side reaction is reduced, to improve the security performance of electrode material
According to the disclosure in order to further enhance the cycle performance and high rate performance of electrode material, it is preferable that nano metal Oxide further includes aluminium oxide and/or titanium oxide.
In a kind of preferred embodiment of the disclosure, the first nano-metal-oxide be nanometer tungsten oxide, second nanometer Metal oxide is the mixture of nano-titanium oxide and nano aluminium oxide, nanometer tungsten oxide, nano-titanium oxide and nano aluminium oxide The ratio between weight content can be 1:(0.25~1.0): (0.25~1.0), further preferably 1:(0.5~0.8): (0.5~ 0.8).In above-mentioned preferred embodiment, the nano-metal-oxide of the mixture formation of tungsten oxide, titanium oxide and aluminium oxide Shell can more effectively prevent and to be capable of forming the more stable positive electrode particle of structure with electrolyte contacts in inner nuclear material, It prevents from easily undergoing phase transition during the ion deinsertion of nickel-cobalt lithium manganate material lithium under high voltages and leading to structure collapses, thus into One step improves the cycle performance and high rate performance of electrode material.
According to the disclosure, the average grain diameter of composite material of core-shell structure can change in a big way, it is preferable that average Partial size can be 8~14 μm, preferably 9~13 μm, further preferably 10~12 μm, to further increase the electricity of positive electrode Chemical property.Wherein, the average grain diameter of composite material of core-shell structure can observe random any 100 by scanning electron microscope (SEM) A composite material of core-shell structure particle measures particle size values respectively, and the average value of partial size is the average grain of composite material of core-shell structure Diameter.
Further, the size of the kernel of composite material of core-shell structure and shell can change in larger range, preferably feelings Under condition, kernel is the second particle of nickle cobalt lithium manganate, and the average grain diameter of the nickle cobalt lithium manganate second particle as kernel can be 9 ~13 μm, further preferably 10~12 μm, second particle refers to the particle that nickle cobalt lithium manganate primary particle agglomerates into, wherein The partial size of nickle cobalt lithium manganate primary particle is, for example, 0.4~1 μm.
According to the disclosure, the thickness of the shell containing nano-metal-oxide can be 2~100nm, further preferably 4 ~20nm.Wherein, the side of FIB (focused ion beam) or directly section grinding can be used within the scope of one in the thickness of shell Method is made section exposure, is then observed using tools such as TEM, and any 10 positive electrode particles is taken to measure shell thickness respectively The upper limit value and lower limit value of degree, then taking the average value of shell thickness upper limit value and lower limit value respectively is the thickness model of shell It encloses.
According to the disclosure, the constituent content of nickle cobalt lithium manganate particle can change in a big way, it is preferable that nickel cobalt manganese It can have higher nickel content in sour lithium particle, to improve the energy density of positive electrode；Such as in one embodiment, The chemical formula of nickle cobalt lithium manganate can be Li (NixCoyMn1-x-y)O2, wherein 0.6≤x≤0.9,0.05≤y≤0.2, further Ground, 0.65≤x≤0.8,0.08≤y≤0.2.
According to the disclosure, the grain structure of composite material of core-shell structure is stablized, the XRD spectra of composite material of core-shell structure (003) the peak intensity I of diffraction maximum003(104) the peak intensity I of diffraction maximum104Ratio I003/I104It can be 1.1≤I003/I104 ≤ 1.5, preferably 1.2≤I003/I104≤1.4；The half-peak breadth of (104) diffraction maximum of composite material of core-shell structure can be 0.2 ~0.26, preferably 0.22~0.25.
According to the disclosure, in the composite material of core-shell structure, the relative amount of nuclear material and shell material can be in larger model Interior variation is enclosed, further, the composite material of core-shell structure that kernel and shell sizes are suitable in order to obtain, nickle cobalt lithium manganate particle With weight ratio (the i.e. weight of inner nuclear material and Shell Materials of the first nano-metal-oxide and the second nano-metal-oxide Than) can be 1:(0.0005~0.005): (0.00025~0.0025), preferably 1:(0.0015~0.003): (0.0005 ~0.001), further preferably 1:(0.002~0.0026): (0.0006~0.0008).
Disclosure second aspect provides the method for the anode material for lithium-ion batteries of preparation disclosure first aspect, this method Include the following steps: S1, after mixing nickel-cobalt-manganese ternary presoma with lithium source progress first, is then carried out in oxygen-containing gas atmosphere First roasting, first roasting temperature be 800~950 DEG C, preferably 840~900 DEG C, the time be 10~20h, preferably 12~ 18h obtains the first product of roasting；S2 makes the first product of roasting and the first nano-metal-oxide and the second nano metal oxide Object carry out second mixing after carry out second roasting, second roasting temperature be 400~600 DEG C, preferably 450~550 DEG C, the time For 8~16h, preferably 9~14h, anode material for lithium-ion batteries is obtained.Further, with elemental metal, the first nanogold The dosage weight ratio for belonging to oxide and the second nano-metal-oxide can be 1:(0.5~2.0).
The cladding process of disclosed method is simple and easy, and production cost is low, is suitable for being mass produced.
According to the disclosure, carrying out the first mixing and the second mixed method and condition can be this field routine.In order to Nickel-cobalt-manganese ternary presoma is promoted to be sufficiently mixed with lithium source, in one embodiment, first is mixed into dry mixed, such as It is mixed in ball mill, high-speed mixer or three-dimensional mixer, mixed revolving speed can be 1000~1500r/min, preferably For 1100~1300r/min, incorporation time can be 15~50min, preferably 20~40min；Second is mixed into dry mixed, Revolving speed be 1000~1500r/min, preferably 1100~1300r/min, incorporation time be 15~50min, preferably 20~ 40min。
According to the disclosure, lithium source can be this field conventional kind, such as lithium source can be for selected from lithium carbonate, hydroxide Lithium, lithium acetate or lithium fluoride, or be the two or three in them or four combination.
According to the disclosure, nickel-cobalt-manganese ternary presoma can be this field conventional kind, in one embodiment, nickel cobalt The structural formula of manganese ternary precursor can be NixCoyMn1-x-y(OH)2, wherein 0.6≤x≤0.9,0.05≤y≤0.2.Nickel cobalt manganese Ternary precursor can be commercial products, for example, be purchased from the source Guizhou Zhong Weizheng company, new material Co., Ltd article number The nickel-cobalt-manganese ternary presoma of ZWN002-1807001-3.
According to the disclosure, lithium source and the relative usage of nickel-cobalt-manganese ternary presoma can change in a big way, preferably Ground, lithium source and the dosage molar ratio of nickel-cobalt-manganese ternary presoma can be (1.005~1.010) in terms of elemental lithium: 1, more preferably For (1.010~1.060): 1；The relative usage of nano-metal-oxide and the first product of roasting can become in a big way Change, with elemental metal, the dosage weight of the first nano-metal-oxide, the second nano-metal-oxide and the first product of roasting Than that can be (0.0005~0.005): (0.00025~0.0025): 1, more preferably (0.001~0.003): (0.0005~ 0.002):1。
According to the disclosure, the first roasting can carry out under oxygen-containing gas atmosphere, and the oxygen content of oxygen-containing gas atmosphere can Think 50~100mol%, preferably 60~80mol%, within the scope of above-mentioned preferred oxygen content, preparation cost is lower, together When guarantee material can fully reacting, inhibit cationic mixing, improve the efficiency for charge-discharge of material.
In disclosed method, the partial size of the first nano-metal-oxide and the second nano-metal-oxide can compared with Variation in a wide range of, in order to further increase coating modification effect, the structure that raising prepares product composite material of core-shell structure is steady It is qualitative, it is preferable that the partial size of the first nano-metal-oxide can be 10~100nm, more preferably 20~50nm；Second nanometer The partial size of metal oxide can be 10~100nm, more preferably 20~50nm.
Further, in the disclosure preferably a kind of embodiment, the first nano-metal-oxide is nanometer tungsten oxide, Second nano-metal-oxide is the mixture of nano-titanium oxide and nano aluminium oxide；With elemental metal nanometer tungsten oxide, receive The weight ratio of rice titanium oxide and nano aluminium oxide can be 1:(0.25~1.0): (0.25~1.0)；Nanometer tungsten oxide, nanometer The ratio between partial size of titanium oxide and nano aluminium oxide can be 1:(0.2~1.0): (0.2~1.0).In above-mentioned preferred embodiment party In formula, cooperated using particular types, the first nano-metal-oxide with when partial size and the second nano-metal-oxide, to nickel Cobalt manganic acid lithium particle is coated, and the stable structure for the composite material of core-shell structure being prepared can be further effectively improved Property, effect is obviously improved to the specific capacity, high rate performance and the cycle performance that improve positive electrode.
According to the disclosure, in order to obtain the first suitable product of roasting of particle size, be convenient for nano-metal-oxide Cladding process, this method can also include: before step S2, the step of the first product of roasting is crushed, sieved；Powder The partial size of first product of roasting broken, after screening can be 8~14 μm.Wherein, being crushed and sieved can be normal for this field Rule method, details are not described herein again；The partial size of first product of roasting refers to D50Partial size, D50The test method of partial size can be ability Domain conventional method.
According to the disclosure, the suitable positive electrode of particle size, this method can also include: by the second roasting in order to obtain Obtained material is crushed, is sieved, and anode material for lithium-ion batteries is obtained.Being crushed and sieved can be conventional for this field Method, details are not described herein again.
The disclosure third aspect provides a kind of lithium ion cell positive, which includes the lithium ion of disclosure first aspect Cell positive material.
According to the disclosure, lithium ion cell positive may include plus plate current-collecting body and coated on the anode on plus plate current-collecting body Material layer, positive electrode material layer may include the above-mentioned positive electrode including composite material of core-shell structure, conductive agent and binder, glue Tying agent can be the common binder of anode, such as fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), poly- four One or more of vinyl fluoride (PTFE) and butadiene-styrene rubber (SBR).Conductive agent can be the common conductive agent of anode, such as acetylene Black, carbon nanotube, carbon fiber, carbon black etc..
Disclosure fourth aspect provides a kind of lithium ion battery, which includes the lithium ion battery of the disclosure third aspect Anode.
According to the disclosure, what the structure of lithium ion battery can be conventional for this field, such as may include above-mentioned lithium from Sub- anode, cathode and electrolyte, cathode can be the cathode of lithium ion battery conventional kind, and electrolyte can be lithium ion Conventional kind in battery, details are not described herein again.
Illustrate the disclosure by the following examples, but therefore the disclosure is not any way limited.Under the disclosure It states in embodiment, ternary precursor Ni0.65Co0.20Mn0.15(OH)2Purchased from the Guizhou source Zhong Weizheng new material Co., Ltd；Nano oxygen Change aluminium, nanometer tungsten oxide, nano-titanium oxide and nano silicon oxide and is purchased from Yicheng Jing Rui new material Co., Ltd, partial size difference respectively For 30nm, remaining reagent is commercial products.
Embodiment 1
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2With lithium carbonate according to the molar ratio of 1:1.025 in mixed at high speed It is uniformly mixed on machine (being purchased from Chuan Tian Machinery Manufacturing Co., Ltd.), revolving speed 1200r/min, incorporation time 30min；It mixes Material be sintered 14 hours at 870 DEG C in atmosphere furnace, keep furnace in oxygen content after 50% or more, material Temperature fall, Ground, 400 mesh screens sieving, obtains a roasted product；By an above-mentioned roasted product and covering nano aluminium oxide (grain Diameter is 30nm), nanometer tungsten oxide (partial size 30nm) in high-speed mixer (Chuan Tian Machinery Manufacturing Co., Ltd.) be uniformly mixed, Revolving speed is 1200r/min, incorporation time 30min, nano aluminium oxide, nanometer tungsten oxide covering amount be aluminium element, wolfram element Weight ratio with a roasted product is respectively 0.0005:1,0.001:1；Cladding material is placed in Muffle furnace at 550 DEG C and is sintered It 10 hours, is sieved after material Temperature fall through grinding, 400 mesh screens, obtains the lithium-ion electric that two firing product are the present embodiment Pond positive electrode.
Embodiment 2
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving obtains a roasted product；By above-mentioned primary roasting It burns product to be uniformly mixed with covering nano-titanium oxide, nanometer tungsten oxide, mixing condition is same as Example 1, nano-titanium oxide The covering amount of (partial size 30nm), nanometer tungsten oxide (partial size 30nm) is the weight of titanium elements, wolfram element and a roasted product Amount is than being respectively 0.0005:1,0.001:1；Cladding material is placed in Muffle furnace at 550 DEG C and is sintered 10 hours, material Temperature fall By grinding, the sieving of 400 mesh screens, the anode material for lithium-ion batteries that two firing product are the present embodiment is obtained.
Embodiment 3
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving obtains a roasted product；By above-mentioned primary roasting Product to be burnt to be uniformly mixed with covering nano aluminium oxide, nano-titanium oxide, nanometer tungsten oxide, mixing condition is same as Example 1, Nano aluminium oxide (partial size 30nm), nano-titanium oxide (partial size 30nm), nanometer tungsten oxide (partial size 30nm) covering amount Weight ratio for, aluminium element, titanium elements, wolfram element and a roasted product is respectively 0.0005:1,0.0005:1,0.001:1； Cladding material is placed in Muffle furnace at 550 DEG C and is sintered 10 hours, is sieved, obtains through grinding, 400 mesh screens after material Temperature fall Two firing product are the anode material for lithium-ion batteries of the present embodiment.
Embodiment 4
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving obtains a roasted product；By above-mentioned primary roasting Product to be burnt to be uniformly mixed with covering nano aluminium oxide, nano-titanium oxide, nanometer tungsten oxide, mixing condition is same as Example 1, Nano aluminium oxide (partial size 30nm), nano-titanium oxide (partial size 30nm), nanometer tungsten oxide (partial size 30nm) covering amount Weight ratio for, aluminium element, titanium elements, wolfram element and a roasted product is respectively 0.0005:1,0.0008:1,0.001:1； Cladding material is placed in Muffle furnace at 550 DEG C and is sintered 10 hours, is sieved, obtains through grinding, 400 mesh screens after material Temperature fall Two firing product are the anode material for lithium-ion batteries of the present embodiment.
Embodiment 5
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving obtains a roasted product；By above-mentioned primary roasting Product to be burnt to be uniformly mixed with covering nano aluminium oxide, nano-titanium oxide, nanometer tungsten oxide, mixing condition is same as Example 1, Nano aluminium oxide (partial size 30nm), nano-titanium oxide (partial size 30nm), nanometer tungsten oxide (partial size 30nm) covering amount Weight ratio for, aluminium element, titanium elements, wolfram element and a roasted product is respectively 0.0005:1,0.0015:1,0.001:1； Cladding material is placed in Muffle furnace at 550 DEG C and is sintered 10 hours, is sieved, obtains through grinding, 400 mesh screens after material Temperature fall Two firing product are the anode material for lithium-ion batteries of the present embodiment.
Embodiment 6
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving obtains a roasted product；By above-mentioned primary roasting Product to be burnt to be uniformly mixed with covering nano aluminium oxide, nano-titanium oxide, nanometer tungsten oxide, mixing condition is same as Example 1, Nano aluminium oxide (partial size 30nm), nano-titanium oxide (partial size 30nm), nanometer tungsten oxide (partial size 30nm) covering amount Weight ratio for, aluminium element, titanium elements, wolfram element and a roasted product is respectively 0.0005:1,0.0008:1,0.001:1； Cladding material is placed in Muffle furnace at 500 DEG C and is sintered 10 hours, is sieved, obtains through grinding, 400 mesh screens after material Temperature fall Two firing product are the anode material for lithium-ion batteries of the present embodiment.
Embodiment 7
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving obtains a roasted product；By above-mentioned primary roasting Product to be burnt to be uniformly mixed with covering nano aluminium oxide, nano-titanium oxide, nanometer tungsten oxide, mixing condition is same as Example 1, Nano aluminium oxide (partial size 50nm), nano-titanium oxide (partial size 50nm), nanometer tungsten oxide (partial size 30nm) covering amount Weight ratio for, aluminium element, titanium elements, wolfram element and a roasted product is respectively 0.0005:1,0.0008:1,0.0007: 1；Cladding material is placed in Muffle furnace at 550 DEG C and is sintered 10 hours, is sieved, obtains through grinding, 400 mesh screens after material Temperature fall It is the anode material for lithium-ion batteries of the present embodiment to two firing product.
Embodiment 8
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving obtains a roasted product；By above-mentioned primary roasting It burns product to be uniformly mixed with covering nano silicon oxide (partial size 40nm), nanometer tungsten oxide (partial size 50nm), mixing condition It is same as Example 1, nano silicon oxide, nanometer tungsten oxide covering amount be the weight of element silicon, wolfram element and a roasted product Amount is than being respectively 0.0005:1,0.001:1；Cladding material is placed in Muffle furnace at 550 DEG C and is sintered 10 hours, material Temperature fall By grinding, the sieving of 400 mesh screens, two firing product are obtained.
Comparative example 1
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving, obtaining a roasted product is this comparative example Anode material for lithium-ion batteries.
Comparative example 2
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It mixes with lithium carbonate according to the molar ratio of 1:1.025, adds simultaneously Enter nano aluminium oxide (partial size 30nm), nano-titanium oxide (partial size 30nm), nanometer tungsten oxide (partial size 30nm), additional amount According to metallic element poidometer, mixture is calculated according to 25% burn tinctuer, three kinds of nano-metal-oxides (aluminium elements, titanium member Element, wolfram element) it with the weight ratio of a roasted product is 0.0005:1,0.0008:1,0.001:1 respectively, mixing condition and reality It is identical to apply example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps in furnace oxygen content 50% or more, After material Temperature fall, obtained after the sieving of ground, 400 mesh screens doping type finished product be the lithium ion battery of this comparative example just Pole material.
Comparative example 3
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2It is uniformly mixed, mixes according to the molar ratio of 1:1.025 with lithium carbonate Conjunction condition is same as Example 1；The material mixed is sintered 14 hours at 870 DEG C in atmosphere furnace, keeps oxygen content in furnace After 50% or more, material Temperature fall, ground, 400 mesh screens sieving obtains a roasted product；By above-mentioned primary roasting It burns product to be uniformly mixed with covering nanometer tungsten oxide (partial size 30nm), mixing condition is same as Example 1, nanometer tungsten oxide Covering amount are as follows: the weight ratio of wolfram element and a roasted product is respectively 0.001:1；Cladding material is placed in 550 in Muffle furnace It is sintered 10 hours, is sieved after material Temperature fall through grinding, 400 mesh screens, obtaining two firing product is the present embodiment at DEG C Anode material for lithium-ion batteries.
Comparative example 4
By ternary precursor Ni0.65Co0.20Mn0.15(OH)2With lithium carbonate according to the molar ratio of 1:1.025 in mixed at high speed It is uniformly mixed on machine (Chuan Tian Machinery Manufacturing Co., Ltd.), revolving speed 1200r/min, incorporation time 30min；The object mixed Material is sintered 14 hours at 870 DEG C in atmosphere furnace, and oxygen content is after 50% or more, material Temperature fall in holding furnace, through grinding Mill, the sieving of 400 mesh screens, obtain a roasted product；By an above-mentioned roasted product and covering nano aluminium oxide, (partial size is 30nm), nanometer tungsten oxide (partial size 30nm) is uniformly mixed in high-speed mixer (Chuan Tian Machinery Manufacturing Co., Ltd.), revolving speed For 1200r/min, incorporation time 30min, nano aluminium oxide, nanometer tungsten oxide covering amount be aluminium element, wolfram element and one The weight ratio of secondary roasted product is respectively 0.004:1,0.001:1；It is small that cladding material is placed in Muffle furnace sintering 10 at 550 DEG C When, be sieved after material Temperature fall through grinding, 400 mesh screens, the two firing product that obtain be the lithium ion battery of the present embodiment just Pole material.
Testing example 1
The structure for the anode material for lithium-ion batteries that Examples 1 to 8 and comparative example 1~4 obtain is tested, wherein The average grain diameter of composite material of core-shell structure is enterprising scanning electron microscope (being purchased from FEI Co., model Nova NanoSEM 450) Row test, the shell thickness of composite material of core-shell structure transmission Electronic Speculum on the scene (are purchased from FEI Co., model Tecnai G2F30 it is tested on), composite material of core-shell structure I003/I104(104) half-peak breadth of diffraction maximum is in X-ray diffractometer (purchase It is tested from Japanese company, Shimadzu Corporation, model XRD-7000S), test result is listed in table 1.
Table 1
Testing example 2
The anode material for lithium-ion batteries obtained to Examples 1 to 8 and comparative example 1~4 carries out battery specific capacity, forthright again Table 2 can be listed in cycle performance test, test result.
Table 2
3 cycle performance test result of table
By embodiment in table 2 and table 3 and comparative example data comparison it is found that the disclosure contains the compound nickel cobalt manganese of core-shell structure The positive electrode of sour lithium, structural stability is good, and the high rate performance of the half-cell prepared using the positive electrode of the disclosure is recycled Performance and specific capacity are promoted, and the comprehensive performance of battery is improved.This is mainly due to the metal oxygens of material surface cladding Compound has good electron conductivity, and by reducing contact of the electrolyte with positive electrode, stabilizes material structure, protect The transmission channel for protecting lithium ion, so that the high rate performance of positive electrode is largely improved, while the cyclicity of material It can be also obviously improved.
The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure Monotropic type, these simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the disclosure to it is various can No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally Disclosed thought equally should be considered as disclosure disclosure of that.

Claims (12)

1. a kind of modified anode material for lithium-ion batteries of compound coating, which is characterized in that the positive electrode includes core-shell structure Composite material, the composite material of core-shell structure include kernel and the shell for being coated on the core surface, and the kernel is nickel Cobalt manganic acid lithium particle, the shell include the first nano-metal-oxide and the second nano-metal-oxide, described first nanometer Metal oxide is nanometer tungsten oxide, and second nano-metal-oxide includes nano aluminium oxide, nano silicon oxide, nano oxygen Change at least one of titanium, nano zircite and nano magnesia, with elemental metal, first nano-metal-oxide and The weight ratio of second nano-metal-oxide is 1:(0.5~2.0).
2. positive electrode according to claim 1, wherein the average grain diameter of the composite material of core-shell structure is 8~14 μ m。
3. positive electrode according to claim 1 or 2, wherein the kernel is the second particle of nickle cobalt lithium manganate, described The chemical formula of nickle cobalt lithium manganate is Li (NixCoyMn1-x-y)O2, wherein 0.6≤x≤0.9,0.05≤y≤0.2.
4. positive electrode according to claim 1, wherein spread out (003) of the XRD spectra of the composite material of core-shell structure Penetrate the peak intensity I at peak003(104) the peak intensity I of diffraction maximum104Ratio I003/I104For 1.1≤I003/I104≤1.5；It is described The half-peak breadth of (104) diffraction maximum of composite material of core-shell structure is 0.2~0.26.
5. positive electrode according to claim 1, wherein the nickle cobalt lithium manganate particle and the first nano metal oxygen Compound and the weight ratio of second nano-metal-oxide are 1:(0.0005~0.005): (0.00025~0.0025).
6. positive electrode according to claim 1, wherein second nano-metal-oxide is nano-titanium oxide and receives The mixture of rice aluminium oxide；With the weight ratio of elemental metal nanometer tungsten oxide, nano-titanium oxide and nano aluminium oxide for 1: (0.25~1.0): (0.25~1.0).
7. the method for preparing anode material for lithium-ion batteries described in any one of claim 1~6, which is characterized in that should Method includes the following steps:
S1 after mixing nickel-cobalt-manganese ternary presoma with lithium source progress first, then carries out the first roasting in oxygen-containing gas atmosphere, The temperature of first roasting is 800~950 DEG C, and the time is 10~20h, obtains the first product of roasting；
S2 carries out first product of roasting and first nano-metal-oxide and second nano-metal-oxide The second roasting is carried out after second mixing, the temperature of second roasting is 400~600 DEG C, and the time is 8~16h, obtains the lithium Ion battery positive electrode；
Wherein, in terms of elemental lithium the dosage molar ratio of the lithium source and the nickel-cobalt-manganese ternary presoma be (1.010~ 1.060): 1, with elemental metal, first nano-metal-oxide, second nano-metal-oxide and described first The dosage weight ratio of product of roasting is (0.0005~0.005): (0.00025~0.0025): 1.
8. according to the method described in claim 7, wherein, the oxygen content of the oxygen-containing gas atmosphere is 50~100mol%；
The partial size of first nano-metal-oxide is 10~100nm, and the partial size of second nano-metal-oxide is 10 ~100nm；
The lithium source is selected from lithium carbonate, lithium hydroxide, lithium acetate or lithium fluoride, or for both in them or three or four Combination；
The structural formula of the nickel-cobalt-manganese ternary presoma is NixCoyMn1-x-y(OH)2, wherein 0.6≤x≤0.9,0.05≤y≤ 0.2。
9. according to the method described in claim 7, first nano-metal-oxide be nanometer tungsten oxide, described second nanometer Metal oxide is the mixture of nano-titanium oxide and nano aluminium oxide；With nanometer tungsten oxide described in elemental metal, described receive The weight ratio of rice titanium oxide and the nano aluminium oxide is 1:(0.25~1.0): (0.25~1.0)；The nanometer tungsten oxide, The ratio between partial size of the nano-titanium oxide and the nano aluminium oxide is 1:(0.2~1.0): (0.2~1.0).
10. according to the method described in claim 7, wherein, this method further include:
Before step S2, the step of first product of roasting is crushed, is sieved；First after the crushing, screening The partial size of product of roasting is 8~14 μm；And/or
The material that second roasting obtains is crushed, is sieved, the anode material for lithium-ion batteries is obtained.
11. a kind of lithium ion cell positive, which is characterized in that the anode includes lithium described in any one of claim 1~6 Ion battery positive electrode.
12. a kind of lithium ion battery, which is characterized in that the battery includes lithium ion cell positive described in claim 11.
CN201811314411.2A 2018-11-06 2018-11-06 Modified anode material for lithium-ion batteries of compound coating and preparation method thereof, anode and lithium ion battery Pending CN109411733A (en)

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Application publication date: 20190301