CN106910882A - A kind of lithium ion battery preparation method of large single crystal layered cathode material - Google Patents

A kind of lithium ion battery preparation method of large single crystal layered cathode material Download PDF

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CN106910882A
CN106910882A CN201710216044.1A CN201710216044A CN106910882A CN 106910882 A CN106910882 A CN 106910882A CN 201710216044 A CN201710216044 A CN 201710216044A CN 106910882 A CN106910882 A CN 106910882A
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lithium
cathode material
single crystal
large single
preparation
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CN106910882B (en
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侯配玉
李凤
邓小龙
徐锡金
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University of Jinan
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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
    • 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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Abstract

The present invention discloses a kind of preparation method of lithium ion battery large single crystal layered cathode material, and micron order large single crystal layered cathode material is prepared by the new method based on presoma substep plus lithium：Ni Co Mn presomas are mixed with the lithium source of stoichiometric proportion first, wherein the mol ratio of elemental lithium and transition metal is between 01, calcine at high temperature, the Spinel for now being formed due to lacking lithium contributes to a fusion for crystal grain and growth, obtains crystal grain of the larger-size compound phase of micron order or pure phase；Secondly to the lithium source that metering ratio is supplemented in the crystal grain of above-mentioned preparation so that elemental lithium and mol ratio Li/Ni Co Mn=(1+z)/(1 z) of transition metal, large single crystal layered cathode material is obtained after calcining at high temperature.Compared to general layer shape positive electrode, the micron order large single crystal ternary material has tap density and compacted density higher, the volume energy density of layered cathode material is remarkably improved, the need for meeting in the market to volume energy density lithium ion battery high.

Description

A kind of lithium ion battery preparation method of large single crystal layered cathode material
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of micron order large single crystal layered lithium ion battery is just Pole material and preparation method thereof.
Background technology
Lithium ion battery has been widely used " 3C " portable electric appts as the energy storage technology of high-energy-density, and by Walk and expanded to Large Copacity, high power system such as electric tool and automobile, high-efficiency energy-storage and military system.It is excellent compared to combination property Different Carbon anode, high cost, the positive electrode of low capacity limit the lifting of performance of lithium ion battery and its in Large Copacity, Gao Gong The extensive use of rate system, therefore developing low-cost, high performance positive electrode are heavy for promoting lithium ion battery development to have Big meaning.
1999, Liu and its partner prepared and report ternary layered positive electrode LiMn earliestxCoyNi1-x-yO2(0< X, y<1,0<x+y<1) capacity and excellent cyclical stability higher, is shown.LiNixCoyMn1-x-yO2It is LiCoO2- LiNiO2-LiMnO2The solid solution that three is formed, it largely combines the advantage of these three stratified materials. LiNixCoyMn1-x-yO2With LiCoO2With identical α-NaFeO2Type layer structure, wherein Li+Occupy 3a, transition metal from Son occupies 3b, O2-Occupy 6c.
Hereafter, Ohzuku in 2001 etc. is prepared for the stratified material LiMn of Mn-Co-Ni equal proportions1/3Co1/3Ni1/3O2, this Planting layered cathode material has specific discharge capacity high, excellent big multiplying power discharging capacity and security feature, causes follow-up getting over Carry out more concerns.2002, Jahn etc. further synthesized the stratified material LiNi of serial Ni/Mn equal proportionsxCo1- 2xMnxO2(0≤x≤1/2).Ni, Co and Mn are respectively+2 ,+3 and+4 valencys, wherein Mn in this kind of material4+Without electrochemistry Activity, being capable of stable laminated structure, Ni in electrochemical process2+And Co3+Participate in electrochemical reaction, its oxidation-reduction pair point Wei not Ni2+/Ni3+/Ni4+And Co3+/Co4+.Therefore LiNixCo1-2xMnxO2(0≤x≤1/2) material equally has excellent electrification Learn performance.
Lithium-rich phase Li1+zM1-zO2(M is a kind of or multivalent transition metal element, particularly M=Mn1-x-yNixCoy,z>0) Show excellent chemical property, such as height ratio capacity (>260mAh g-1) and new charge-discharge mechanism, as lithium-ion electric One of study hotspot of pond positive electrode.By the research of more than ten years, researcher to the structure of rich lithium phase layered oxide material, Performance, charge-discharge mechanism and its structure-activity relationship have certain cognition.Bruce etc. confirms to be sent out when 4.50V platforms are charged to Raw Li+Abjection, simultaneous O2Release, in addition also along with transition metal ions by surface while Surface Oxygen is lost in Moving and occupying Li internally+In the room caused of abjection, thus discharge process behind, only major part Li+Can be embedded To material of main part, this causes lithium-rich material irreversible capacity first higher.
Although layered cathode material Li1+z[Ni1-x-yCoxMny]1-zO2With high power capacity, have extended cycle life, high rate performance it is excellent Different and inexpensive the advantages of, but its volume energy density can not still catch up with and surpass the layered cathode material of current widespread commercial LiCoO2, this largely limits layered cathode material Li1+z[Ni1-x-yCoxMny]1-zO2In lithium-ion battery system Extensive use.
The content of the invention
In order to solve above-mentioned layered cathode material Li1+z[Ni1-x-yCoxMny]1-zO2Volume energy density is relatively low not Foot, the need for meeting in the market to volume energy density lithium ion battery high, the present invention is proposed based on presoma substep plus lithium Prepare micron order large single crystal layered cathode material Li1+z[Ni1-x-yCoxMny]1-zO2New method.
The concrete technical scheme that the present invention is used is as follows：
A kind of lithium ion battery preparation method of large single crystal layered cathode material, the knot of the large single crystal layered cathode material Structure formula is Li1+z[Ni1-x-yCoxMny]1-zO2, wherein, 0<x、y<1,0≤z≤0.2,0<x+y<1, the preparation method include with Lower step：
Ni-Co-Mn presomas are mixed with lithium source first, wherein the mol ratio of elemental lithium and transition metal is in 0-1 Between, high-temperature calcination now forms Spinel because elemental lithium is not enough, Spinel contribute to a fusion for crystal grain with Growth, obtains crystal grain of crystal grain of the larger-size compound phase of micron order or pure phase；A para-crystal of preparation is stated then up The lithium source of stoichiometric proportion is supplemented in grain so that the mol ratio Li/Ni-Co-Mn=(1+z) of elemental lithium and transition metal/ (1-z)~[(1+z)/(1-z)+0.05], lithium ion battery large single crystal layered cathode material is can obtain after calcining at high temperature Material.
Preferably, the molecular formula Li of large single crystal layered cathode material1+z[Ni1-x-yCoxMny]1-zO2, work as y<When 0.5,0≤z ＜ 0.05；When y >=0.5,0.05≤z≤0.2.
Preferably, Ni-Co-Mn presomas are prepared as technology well-known to those skilled in the art, it is preferred that can pass through Presoma [Ni is prepared using coprecipitation method1-x-yCoxMny](OH)2、[Ni1-x-yCoxMny]CO3Or [Ni1-x-yCoxMny]Ox。
Preferably, the preparation method of presoma includes one or more in hydroxide, carbonate or oxalates method.
Preferably, the lithium source is one or more in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and lithium oxalate.
Preferably, calcination atmosphere is air or oxygen atmosphere.
Preferably, the condition of first time high-temperature calcination be 900-1050 DEG C at calcine 2-24h.
Preferably, the condition of second high-temperature calcination be 800-950 DEG C at calcine 2-24h.
Preferably, high-temperature calcination atmosphere is air or oxygen atmosphere.
Preferably, the heating rate of material is 1-10 DEG C/min.
The present invention also provide the large single crystal layered cathode material that a kind of use above method prepares and its lithium from Application in sub- battery.
Compared with prior art, the technical solution adopted by the present invention has the advantages that：
Lithium is added to prepare the ternary layered positive electrode of micron order large single crystal present invention firstly provides presoma substep is based on Li1+z[Ni1-x-yCoxMny]1-zO2New method, compared to general layer shape positive electrode, the micron order for preparing in this way is big Monocrystalline layered cathode material has tap density and compacted density higher, can meet lithium ion battery to volume energy density high Requirement；The method step is simple, gentle simultaneously, is adapted to large-scale industrial production.
Brief description of the drawings
The Figure of description for constituting a part of the invention is used for providing a further understanding of the present invention, of the invention to show Meaning property and its illustrates, for explaining the present invention, not constitute inappropriate limitation of the present invention embodiment.
Fig. 1 is to be co-precipitated the presoma [Ni prepared by route1/3Co1/3Mn1/3](OH)2SEM.
Fig. 2 is that embodiment 2 is schemed with the SEM of comparative example 1.
Fig. 3 is the XRD of embodiment 2 and comparative example 1.
Fig. 4 is the first charge-discharge curve of embodiment 2 and cycle performance curve.
Specific embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the present invention.Unless another Indicate, all technologies used herein and scientific terminology are with usual with general technical staff of the technical field of the invention The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to illustrative embodiments of the invention.As used herein, unless the context clearly indicates otherwise, otherwise singulative Be also intended to include plural form, additionally, it should be understood that, when in this manual use term "comprising" and/or " bag Include " when, it indicates existing characteristics, step, operation and/or combinations thereof.
As background technology is introduced, there is layered cathode material Li in the prior art1+z[Ni1-x-yCoxMny]1-zO2Body The product relatively low deficiency of energy density, in order to solve technical problem as above, the first aspect of the invention, the present invention is first The new method that the ternary layered positive electrode of micron order large single crystal is prepared based on presoma substep plus lithium is proposed, compared to common layer Shape positive electrode, the micron order large single crystal layered cathode material for preparing in this way has tap density higher close with compacting Degree, can meet requirement of the lithium ion battery to volume energy density high, and the general structure of the large single crystal layered cathode material is Li1+z[Ni1-x-yCoxMny]1-zO2, wherein, 0<x、y<1,0≤z≤0.2,0<x+y<1, during the large single crystal refers to the present invention The size of layered cathode material can reach micron order.
The preparation method is comprised the following steps：
First step：It is prepared by the mol ratio according to transition metal shown in the large single crystal layered cathode material formula Ni-Co-Mn presomas；
There are various methods for preparing Ni-Co-Mn presomas in the prior art, from for synthetic effect, the present invention is using altogether Intermediate processing synthesizes Ni-Co-Mn presomas, and the type of the presoma includes [Ni1-x-yCoxMny](OH)2、[Ni1-x-yCoxMny] CO3、[Ni1-x-yCoxMny]OxOr [Ni1-x-yCoxMny]C2O4, can be prepared by conventional method of the prior art, for example Respectively by one or more in hydroxide, carbonate or oxalate coprecipitation method.More specifically, for example, embodiment 1 [the Ni of middle synthesis1-x-yCoxMny](OH)2Presoma；Again for example, the method in referring to CN100417595 is prepared [Ni1-x-yCoxMny]CO3。
Second step：The Ni-Co-Mn presomas that above-mentioned steps are obtained are well mixed with lithium source, wherein by elemental lithium with The mol ratio of transition metal is set as 0<Li/Ni-Co-Mn<1,2-24h then is calcined at 900-1050 DEG C of high temperature, this When form Spinel and lamellar phase due to lacking lithium, or all generation Spinels, the presence of Spinel contributes to one The fusion and growth of secondary crystal grain, and then obtain the larger-size crystal grain of compound phase of micron order or crystal grain of pure phase；
Wherein, the compound phase includes Spinel and lamellar phase, and the pure phase refers to Spinel.
In some embodiments of the invention, during high-temperature calcination, the heating rate of material is 1-10 DEG C/min；Calcination atmosphere It is air or oxygen atmosphere.
In some embodiments of the invention, the lithium source is lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and oxalic acid One or more in lithium.
Third step：To supplementing lithium source in the crystal grain that above-mentioned steps are obtained so that elemental lithium in the mixture with Transition metal mol ratio Li/Ni-Co-Mn=(1+z)/(1-z)~(1+z)/(1-z)+0.05, wherein from the material for obtaining Tap density, compacted density and volume energy density angle higher for, it is preferred that work as y<When 0.5,0≤z≤ 0.05；When y >=0.5,0.05≤z≤0.2；High temperature solid state reaction can further occur under high temperature (800~950 DEG C), make Obtain Spinel and be changed into lamellar phase, ultimately form the large single crystal layered cathode material Li of pure phase1+z[Ni1-x-yCoxMny]1-zO2；
After the supplement lithium source so that elemental lithium and transition metal mol ratio Li/Ni-Co-Mn=in mixture (1+z)/(1-z)~(1+z)/(1-z)+0.05, on the basis of the lithium source with stoichiometric proportion, increases some lithium sources in right amount, Purpose is the vapored away lithium source of supplement calcining.
In some embodiments of the invention, during high-temperature calcination, the heating rate of material is 1-10 DEG C/min；Calcination atmosphere It is air or oxygen atmosphere.
In a preferred embodiment of the present invention, the molecular formula of the large single crystal positive electrode is Li [Ni1/3Co1/ 3Mn1/3]O2。
The second aspect of the invention, it is proposed that the large single crystal layered cathode material prepared using above-mentioned technical proposal Material.
Compared to the general layer shape tertiary cathode material for preparing in the prior art, large single crystal positive electrode of the invention Size it is larger, be 3-8 μm.
Compared to the general layer shape tertiary cathode material for preparing in the prior art, large single crystal positive electrode of the invention Tap density obtained significant raising, be 2.82g/cm3And its more than, and then possess compacted density and volume higher Energy density.
The third aspect of the invention, proposes a kind of lithium ion prepared using above-mentioned large single crystal layered cathode material Battery.The lithium ion battery prepared using the large single crystal positive electrode has discharge cycles capability retention high.
In order that obtaining those skilled in the art can clearly understand technical scheme, below with reference to tool The embodiment of body describes technical scheme in detail with comparative example.
Embodiment 1 prepares presoma [Ni1/3Co1/3Mn1/3](OH)2
Weigh 4.38Kg NiSO4·6H2O、4.68Kg CoSO4·7H2O and 2.52Kg MnSO4·H2O compound concentrations are 2M salting liquids 25L.By above-mentioned salting liquid with 1L h-1Speed is added drop-wise to rotating speed in 200rpm continuous stirred tank reactors, while with The NaOH solution of 10M, 11.5 or so, is disappeared completely with pH value in the mixed solution control kettle of the ammonia spirit of 1M to salting liquid Consumption, sediment is centrifuged, is washed, being dried to obtain presoma [Ni1/3Co1/3Mn1/3](OH)2, its SEM is as shown in Figure 1, it is seen that its With more loose structure.
Comparative example 1：
Weigh the presoma [Ni of the preparation of 91.52g embodiments 11/3Co1/3Mn1/3](OH)2With 38.05g LITHIUM BATTERYs Li2CO3 (Li/Ni-Co-Mn=1.03) uniform mixing, is placed in the mixture in Muffle furnace the sintering 12h under 1000 DEG C of air atmospheres and obtains To general layer shape positive electrode Li [Ni1/3Co1/3Mn1/3]O2, shown in its SEM and XRD such as Fig. 2 (a) and Fig. 3 (a).
Embodiment 2：
Weigh the presoma [Ni of the preparation of 91.52g embodiments 11/3Co1/3Mn1/3](OH)2With 12.93g LITHIUM BATTERYs Li2CO3 (Li/Ni-Co-Mn=0.35) uniform mixing, the mixture is placed in Muffle furnace and sinters 10h under 1000 DEG C of air atmospheres, Due to lithium source and the mol ratio Li/Ni-Co-Mn of transition metal<1, therefore spinelle is formd in high temperature solid state reaction Phase [Ni1/3Co1/3Mn1/3]3O4With lamellar phase Li [Ni1/3Co1/3Mn1/3]O2Compound phase, because the presence of Spinel promotes Fast-growth for crystal grain, obtains micro-scale crystal grain (shown in its SEM and XRD such as Fig. 2 (b) and Fig. 3 (b)), further to this 25.12g LITHIUM BATTERYs Li is added in micro-scale crystal grain2CO3So that Li/Ni-Co-Mn=1.03, it is placed in Muffle furnace 900 10h is sintered under DEG C air atmosphere and obtains large single crystal layered cathode material Li [Ni1/3Co1/3Mn1/3]O2, its SEM and XRD such as Fig. 2 C shown in () and Fig. 3 (c), the head week charging and discharging curves and cyclical stability of the electrode prepared with large single crystal layered cathode material are such as Shown in Fig. 4.
It can be seen that layered cathode material Li [Ni obtained by after comparative example 1 is sintered at 1000 DEG C from Fig. 2 (a)1/3Co1/ 3Mn1/3]O2Crystal grain assembles micron-size spherical or elliposoidal second particle for one time, wherein a crystallite dimension is in 1-4 μm of model In enclosing, its XRD tests turn out to be α-NaFeO2Type layer structure, such as Fig. 3 (a).And presoma [Ni1/3Co1/3Mn1/3](OH)2With LITHIUM BATTERY Li2CO3(Li/Ni-Co-Mn=0.35) uniform mixing is placed in Muffle furnace the sintering 10h under 1000 DEG C of air atmospheres and obtains The Li for arriving0.35[Ni1/3Co1/3Mn1/3]O2, its SEM such as Fig. 2 (b), find crystal grain fast-growth in this sintering process, obtain To a 3-8 μm of approximate monodispersed polyhedron-shaped crystal grain, it is compound with Spinel that its XRD tests are shown as lamellar phase Phase, such as Fig. 3 (b)；To continuing to supplement lithium source in the compound phase crystal grain to Li/Ni-Co-Mn=1.03, it is placed in Muffle furnace 900 12h is sintered under DEG C air atmosphere and obtains micron order large single crystal layered cathode material Li [Ni1/3Co1/3Mn1/3]O2, such as Fig. 2 (C) institute Show, its XRD test charts 3 (c) is shown as the layer structure of pure phase.
The large single crystal layered cathode material of embodiment 2 is prepared into electrode, 2032 button cells is assembled, in 2.7-4.5V voltages Charge-discharge test is carried out under interior and 20mA/g current densities, micron order large single crystal stratified material Li [Ni1/3Co1/3Mn1/3]O2It is first All specific discharge capacities are 164.2mAh/g, shown in such as Fig. 4 (a)；Its capability retention after 35 weeks charge and discharge cycles is 73.2%, As shown in Fig. 4 (b).Additionally, the tap density of tap density test display comparison example 1 and embodiment 2 is respectively 2.41 Hes 2.82g/cm3, the prepared micron order large single crystal stratified material Li [Ni of indication confirmation1/3Co1/3Mn1/3]O2Possesses compacting higher close Degree and volume energy density.
In sum, compared to the conventional route for preparing layered cathode material, the disclosure based on presoma substep plus lithium New method prepare micron order large single crystal layered cathode material Li1+z[Ni1-x-yCoxMny]1-zO2New method can significantly improve The tap density of the positive material of stratiform, and then improve the compacted density of electrode and the volume energy density of lithium ion battery.
Embodiment 3：
Weigh the presoma [Ni of the preparation of 91.52g embodiments 11/3Co1/3Mn1/3](OH)2With 12.93g LITHIUM BATTERYs Li2CO3 (Li/Ni-Co-Mn=0.35) uniform mixing, the mixture is placed in Muffle furnace and sinters 8h under 1050 DEG C of oxygen atmospheres, by In lithium source and the mol ratio Li/Ni-Co-Mn of transition metal<1, therefore Spinel is formd in high temperature solid state reaction [Ni1/3Co1/3Mn1/3]3O4With lamellar phase Li1.05[Ni1/3Co1/3Mn1/3]0.95O2Compound phase, due to Spinel presence promote A fast-growth for crystal grain is made, has obtained micro-scale crystal grain, further to addition 29.93g LITHIUM BATTERYs in the micro-scale crystal grain Li2CO3So that Li/Ni-Co-Mn=1.16, it is placed in Muffle furnace and 12h is sintered under 800 DEG C of air atmospheres obtains big list Brilliant layered cathode material Li1.05[Ni1/3Co1/3Mn1/3]0.95O2。
Although above in conjunction with figure, invention has been described, the invention is not limited in above-mentioned specific embodiment party Formula, above-mentioned specific embodiment is only schematical, and rather than restricted, one of ordinary skill in the art is in this hair Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, such as to layered cathode material Li1+z [Ni1-x-yCoxMny]1-zO2(Mg, Zn, Ca, Sr, Cu, Zr, P, Fe, Al, Ga, In, Cr, Ge and Sn are constituted to carry out other elements At least one metal in group) doping and cladding etc., these are belonged within protection of the invention.

Claims (10)

1. a kind of lithium ion battery preparation method of large single crystal layered cathode material, the structure of the large single crystal layered cathode material Formula is Li1+z[Ni1-x-yCoxMny]1-zO2, wherein, 0<x、y<1,0≤z≤0.2,0<x+y<1, it is characterized in that, the preparation method Comprise the following steps：
Ni-Co-Mn presomas are mixed with lithium source first, the wherein mol ratio of elemental lithium and transition metal between 01, High-temperature calcination, now forms Spinel because elemental lithium is not enough, and Spinel contributes to a fusion for crystal grain and growth, Obtain crystal grain of crystal grain of the larger-size compound phase of micron order or pure phase；Benefit in a crystal grain of preparation is stated then up Fill the lithium source of stoichiometric proportion so that mol ratio Li/Ni-Co-Mn=(1+z)/(1-z) of elemental lithium and transition metal ~ [(1+z)/(1-z)+0.05], lithium ion battery large single crystal layered cathode material is can obtain after calcining at high temperature.
2. preparation method as claimed in claim 1, it is characterized in that：Work as y<When 0.5,0≤z ＜ 0.05；When y >=0.5,0.05 ≤z≤0.2。
3. preparation method as claimed in claim 1, it is characterized in that：Presoma [Ni is prepared using coprecipitation method1-x- yCoxMny](OH) 2、[Ni1-x-yCoxMny]CO3Or [Ni1-x-yCoxMny]Ox。
4. preparation method as claimed in claim 1, it is characterized in that：The lithium source be lithium carbonate, lithium hydroxide, lithium nitrate, One or more in lithium acetate and lithium oxalate.
5. preparation method as claimed in claim 1, it is characterized in that：The condition of first time high-temperature calcination is at 900 1050 DEG C Calcine 2 24 h.
6. preparation method as claimed in claim 1, it is characterized in that：The condition of second high-temperature calcination be 800 950 DEG C at forge Burn 2 24 h.
7. preparation method as claimed in claim 1, it is characterized in that：High-temperature calcination atmosphere is air or oxygen atmosphere.
8. preparation method as claimed in claim 1, it is characterized in that：The heating rate of material is 1 10 DEG C/min.
9. the large single crystal layered cathode material for being prepared using the method any one of claim 1 ~ 8.
10. a kind of large single crystal layered cathode material with described in claim 9 is the lithium ion battery of positive pole.
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107528064A (en) * 2017-08-10 2017-12-29 广东邦普循环科技有限公司 A kind of high voltage type class monocrystalline tertiary cathode material and preparation method thereof
CN109037614A (en) * 2018-07-05 2018-12-18 佛山市德方纳米科技有限公司 A kind of high-pressure solid monocrystalline nickel-cobalt-manganese ternary material and preparation method thereof
CN109449436A (en) * 2018-09-13 2019-03-08 厦门大学 A kind of cation vacancy positive electrode and preparation method thereof
CN109786734A (en) * 2018-09-29 2019-05-21 北京泰丰先行新能源科技有限公司 A kind of preparation method of the nickelic positive electrode of lithium secondary battery
CN109952671A (en) * 2017-10-20 2019-06-28 蔚山科学技术院 For the positive active material of lithium secondary battery, preparation method, comprising it electrode and include the lithium secondary battery of the electrode
CN110422892A (en) * 2019-08-08 2019-11-08 青岛新正锂业有限公司 A kind of preparation process of micron order monocrystalline primary particle tertiary cathode material
CN111082041A (en) * 2019-12-27 2020-04-28 中国科学院宁波材料技术与工程研究所 Lithium-rich multi-element positive electrode material, preparation method thereof, positive electrode and lithium ion power battery
CN111106331A (en) * 2019-11-12 2020-05-05 广东邦普循环科技有限公司 Layered-spinel phase composite positive electrode material and preparation method thereof
CN111170369A (en) * 2020-01-08 2020-05-19 济南大学 Lithium manganate or lithium nickel manganese material and preparation method and application thereof
CN113636606A (en) * 2021-07-13 2021-11-12 北京科技大学 Preparation method and application of nickel-rich cobalt-free single crystal cathode material of lithium ion battery
CN113707874A (en) * 2021-08-26 2021-11-26 天津理工大学 Preparation method of single-crystal high-nickel layered cathode material
CN114142037A (en) * 2021-11-19 2022-03-04 天津巴莫科技有限责任公司 Method for preparing ultra-high nickel anode material by adopting gradient lithium supplement and prepared ultra-high nickel anode material
WO2022065935A1 (en) * 2020-09-24 2022-03-31 주식회사 엘지화학 Method for solid-state synthesis of ni-rich lithium composite transition metal oxide cathode active material single particle, ni-rich lithium composite transition metal oxide cathode active material single particle synthesized thereby, and cathode and lithium secondary battery, each containing same
CN114551791A (en) * 2021-07-29 2022-05-27 万向一二三股份公司 Composite positive plate containing single crystal high nickel positive electrode material and all-solid-state battery
CN114678525A (en) * 2022-04-12 2022-06-28 浙江极氪智能科技有限公司 Ternary cathode material, preparation method thereof and lithium ion battery
CN114843458A (en) * 2022-04-07 2022-08-02 青岛乾运高科新材料股份有限公司 High-nickel single crystal cobalt-free anode material and preparation method thereof
CN116598475A (en) * 2023-06-15 2023-08-15 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof and lithium ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103746111A (en) * 2014-01-28 2014-04-23 天津先众科技有限公司 Monocrystal Ni-Co-Mn battery positive pole material and preparing method thereof
CN104868122A (en) * 2015-05-15 2015-08-26 北京理工大学 Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material
CN106410182A (en) * 2016-10-20 2017-02-15 北京理工大学 Preparation method of high compaction density micron-grade monocrystal ternary cathode material
US20170084922A1 (en) * 2011-03-18 2017-03-23 Semiconductor Energy Laboratory Co., Ltd. Lithium ion secondary battery and method for manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170084922A1 (en) * 2011-03-18 2017-03-23 Semiconductor Energy Laboratory Co., Ltd. Lithium ion secondary battery and method for manufacturing the same
CN103746111A (en) * 2014-01-28 2014-04-23 天津先众科技有限公司 Monocrystal Ni-Co-Mn battery positive pole material and preparing method thereof
CN104868122A (en) * 2015-05-15 2015-08-26 北京理工大学 Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material
CN106410182A (en) * 2016-10-20 2017-02-15 北京理工大学 Preparation method of high compaction density micron-grade monocrystal ternary cathode material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZHEN-DONG HUANG 等: "Microscopically porous, interconnected single crystal LiNi1/3Co1/3Mn1/3O2 cathode material for Lithium ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY》 *
沈恒冠 等: "单晶高电压三元的制备及性能研究", 《电源技术》 *

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CN107528064A (en) * 2017-08-10 2017-12-29 广东邦普循环科技有限公司 A kind of high voltage type class monocrystalline tertiary cathode material and preparation method thereof
CN109952671A (en) * 2017-10-20 2019-06-28 蔚山科学技术院 For the positive active material of lithium secondary battery, preparation method, comprising it electrode and include the lithium secondary battery of the electrode
CN109037614A (en) * 2018-07-05 2018-12-18 佛山市德方纳米科技有限公司 A kind of high-pressure solid monocrystalline nickel-cobalt-manganese ternary material and preparation method thereof
CN109037614B (en) * 2018-07-05 2021-06-11 佛山市德方纳米科技有限公司 High-compaction single crystal nickel-cobalt-manganese ternary material and preparation method thereof
CN109449436B (en) * 2018-09-13 2021-03-12 厦门大学 Cation vacancy positive electrode material and preparation method thereof
CN109449436A (en) * 2018-09-13 2019-03-08 厦门大学 A kind of cation vacancy positive electrode and preparation method thereof
CN109786734A (en) * 2018-09-29 2019-05-21 北京泰丰先行新能源科技有限公司 A kind of preparation method of the nickelic positive electrode of lithium secondary battery
CN110422892A (en) * 2019-08-08 2019-11-08 青岛新正锂业有限公司 A kind of preparation process of micron order monocrystalline primary particle tertiary cathode material
CN111106331A (en) * 2019-11-12 2020-05-05 广东邦普循环科技有限公司 Layered-spinel phase composite positive electrode material and preparation method thereof
CN111082041A (en) * 2019-12-27 2020-04-28 中国科学院宁波材料技术与工程研究所 Lithium-rich multi-element positive electrode material, preparation method thereof, positive electrode and lithium ion power battery
CN111170369A (en) * 2020-01-08 2020-05-19 济南大学 Lithium manganate or lithium nickel manganese material and preparation method and application thereof
WO2022065935A1 (en) * 2020-09-24 2022-03-31 주식회사 엘지화학 Method for solid-state synthesis of ni-rich lithium composite transition metal oxide cathode active material single particle, ni-rich lithium composite transition metal oxide cathode active material single particle synthesized thereby, and cathode and lithium secondary battery, each containing same
CN113636606A (en) * 2021-07-13 2021-11-12 北京科技大学 Preparation method and application of nickel-rich cobalt-free single crystal cathode material of lithium ion battery
CN114551791A (en) * 2021-07-29 2022-05-27 万向一二三股份公司 Composite positive plate containing single crystal high nickel positive electrode material and all-solid-state battery
CN114551791B (en) * 2021-07-29 2024-02-02 万向一二三股份公司 Composite positive plate containing monocrystal high-nickel positive electrode material and all-solid-state battery
CN113707874A (en) * 2021-08-26 2021-11-26 天津理工大学 Preparation method of single-crystal high-nickel layered cathode material
CN114142037A (en) * 2021-11-19 2022-03-04 天津巴莫科技有限责任公司 Method for preparing ultra-high nickel anode material by adopting gradient lithium supplement and prepared ultra-high nickel anode material
CN114843458A (en) * 2022-04-07 2022-08-02 青岛乾运高科新材料股份有限公司 High-nickel single crystal cobalt-free anode material and preparation method thereof
CN114843458B (en) * 2022-04-07 2023-11-07 青岛乾运高科新材料股份有限公司 High-nickel monocrystal cobalt-free positive electrode material and preparation method thereof
CN114678525A (en) * 2022-04-12 2022-06-28 浙江极氪智能科技有限公司 Ternary cathode material, preparation method thereof and lithium ion battery
CN114678525B (en) * 2022-04-12 2023-08-18 浙江极氪智能科技有限公司 Ternary positive electrode material, preparation method thereof and lithium ion battery
CN116598475A (en) * 2023-06-15 2023-08-15 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof and lithium ion battery
CN116598475B (en) * 2023-06-15 2023-11-17 宁波容百新能源科技股份有限公司 Positive electrode material, preparation method thereof and lithium ion battery

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