CN110422890A - Anode material for lithium-ion batteries and preparation method thereof and lithium ion cell positive and lithium ion battery - Google Patents
Anode material for lithium-ion batteries and preparation method thereof and lithium ion cell positive and lithium ion battery Download PDFInfo
- Publication number
- CN110422890A CN110422890A CN201910596554.5A CN201910596554A CN110422890A CN 110422890 A CN110422890 A CN 110422890A CN 201910596554 A CN201910596554 A CN 201910596554A CN 110422890 A CN110422890 A CN 110422890A
- Authority
- CN
- China
- Prior art keywords
- lithium
- nickel
- presoma
- nickel cobalt
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides the methods that prelithiation step sintering prepares anode material for lithium-ion batteries, method includes the following steps: the ratio of (1) according to molar ratio 1:M, weighs nickel presoma and lithium salts；(2) nickel presoma is uniformly mixed with the lithium salts for accounting for total amount percentage X, is warming up to t1 DEG C of temperature, is sintered T1 hours；(3) material after the completion of step (2) pre-burning is mixed with remainder (1-X) lithium salts, is warming up to t2 DEG C of temperature, be sintered T2 hours, after broken, screening, obtain positive electrode；Wherein, t2 > t1.Additionally provide a kind of anode material for lithium-ion batteries and a kind of lithium ion cell positive and a kind of lithium ion battery.The method that above-mentioned prelithiation step sintering provided by the invention prepares positive electrode, can not only obtain stable structure, the anode material for lithium-ion batteries of electrochemical performance, and simple process, production process is easily controllable, and production cost is low, is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to field of lithium ion battery, relates more specifically to a kind of prelithiation step sintering and prepare lithium ion battery
The method of positive electrode, and the anode material for lithium-ion batteries that is obtained by this method and including lithium ion cell positive of the invention
The lithium ion cell positive and lithium ion battery of material.
Background technique
Since coming out from nineteen ninety, lithium ion battery is high by its open-circuit voltage, specific energy is high, specific power is high, uses the longevity
The advantages that long, without memory and self discharge is small is ordered, is extensively studied and applies.With the progress of lithium ion battery technology
And development, currently, lithium ion battery is in addition to being widely used to various portable electronic products, also actively to automobile market,
The fields such as medical supplies market, aerospace and national defence are expanded.
Positive electrode is one of important component of lithium ion battery, with the continuous evolution development of lithium electric material and city
Demand of the field to height ratio capacity material, with polynary nickel-cobalt lithium manganate material (LiNixCoyMn1-x-yO2) and rich lithium material
(xLi2MnO3·(1-x)LiMO2；It is one or more kinds of in M=Ni, Co, Mn, Al, V, Cr, Fe) be representative positive electrode
Gradually become the hot spot of research with application.There are many synthetic method of anode material for lithium-ion batteries, mainly have solid phase method, colloidal sol solidifying
Glue method, coprecipitation etc. are a variety of.
The advantage and disadvantage of comprehensive various methods, coprecipitation presoma are industrial widely applied one kind with lithium sintering process
Process.Under this process route, the process of presoma and lithium salts mixed sintering to finally obtained lithium ion battery just
The performance of pole material has conclusive influence.
Coprecipitation presoma common at present is relatively simple with lithium sintering heating mode, usually before sintering heating
Presoma and lithium salts used and additive are disposably uniformly mixed by way of physical mixed, with certain heating rate
Heat temperature raising, the held for some time after reaching target temperature, then Temperature fall, completes entire sintering process.It is once sintered
Process it is relatively easy, it is difficult to fine control accomplished to the synthesis of material, therefore it has been proposed that step sintering scheme, with this
To improve and optimizate original sintering process process.Wherein, presoma is carried out pre-oxidation treatment by application number 201810174055.2
Tertiary cathode material finished product is obtained with lithium source mixed sintering again afterwards.Application number 201810692695.2 is by positive electrode material precursor
With low temperature presintering after lithium source mixing, then the positive electrode after pre-burning is broken up, carries out cladding burning after merging with covering solid phase
Knot, obtains tertiary cathode material finished product.Application number 201710979691.8 is first by the class ball of presoma pre-fired porous honeycomb
Then the pre-burning presoma of shape is added the high-temperature roasting of doped chemical Er, Zr, is obtaining Er, Zr metal ion mixing and doping ternary just
Pole material.These technologies are that presoma or presoma and the mixture of whole lithium sources are carried out a period of time in low-temperature zone mostly
Pre-burning, then high-temperature roasting again obtains positive electrode finished product.
Summary of the invention
It is an object of the present invention on the basis of existing technology, provide that a kind of structural stability is good and chemical property
Excellent anode material for lithium-ion batteries and preparation method thereof.
The study find that sintering process has vital influence to the synthesis of anode material for lithium-ion batteries.Lithium salts
It is lower with the mixture density of presoma, it charges in unit volume saggar less, constrains the raising of production efficiency.It is being sintered
In increase unit volume saggar charge as far as possible, so that it may improve unit production capacity, promote whole production efficiency.It heats up in sintering
During, what different temperatures stage presoma and lithium salts were occurred, which react, has nothing in common with each other.Every kind of different positive electrode has
Its structure forms stable specific temperature node, and a simple temperature increasing schedule can not precisely correspond to different temperatures phase material
Requirement to reaction temperature and time is unfavorable for the performance of final synthetic material.Although more above-mentioned disclosed technology can be
The traditional once sintered process of Optimal improvements to a certain extent, but it is still not careful complete enough to managing and controlling for sintering process
It is kind, it is unfavorable for the performance of the stabilization and performance of cathode material structure.
The shortcomings that for the above-mentioned prior art in terms of sintering process and shortcoming mention to improve existing sintering process
High unit volume saggar fills alms bowl amount, while strengthening the control to Crucial temperature phase, and the present invention provides a kind of new prelithiation point
Sintering process is walked, by the way of step sintering, a certain amount of lithium salts and presoma is added in low temperature section, carries out prelithiation burning
Knot；After the completion of pre-burning, the sintered product of the first step is mixed with remaining lithium salts, secondary high temperature section sintering is carried out, obtains most
Required anode material for lithium-ion batteries finished product eventually.
As a result, according to the first aspect of the invention, the present invention provides prelithiation step sinterings to prepare lithium ion battery just
The method of pole material, method includes the following steps:
(1) according to the ratio of molar ratio 1:M, nickel presoma and lithium salts are weighed；
(2) nickel presoma is uniformly mixed with the lithium salts for accounting for total amount percentage X, is warming up to t1 DEG C of temperature, is sintered T1 hours；
(3) material after the completion of step (2) pre-burning is mixed with remainder (1-X) lithium salts, is warming up to t2 DEG C of temperature, sintering
T2 hours, after broken, screening, obtain positive electrode；
Wherein, t2 > t1.
According to the second aspect of the invention, a kind of anode material for lithium-ion batteries is provided.
According to the third aspect of the invention we, a kind of lithium ion cell positive is provided, wherein the lithium ion cell positive
Contain the aforementioned anode material for lithium-ion batteries.
According to the fourth aspect of the invention, a kind of lithium ion battery is provided, wherein the lithium ion battery includes: anode
And cathode, wherein the just extremely aforementioned lithium ion cell positive.
Anode material for lithium-ion batteries stable structure of the invention, and there is good chemical property, thus it is speculated that reason can
It can be that in low-temperature zone, nickel presoma and lithium salts mainly occur crystallization water dehydration and salt compounds and turn to oxide system
Change, and the formation of a small amount of nickle cobalt lithium manganate phase；Nickel, cobalt, manganese and oxygen when temperature reaches high temperature section, in lithium ion and presoma
Compound is reacted completely, forms stable α-NaFeO2Layer structure nickel-cobalt lithium manganate material.Therefore, this kind of reaction by inference
The rule of progress, the mixing of the method according to the invention substep and pre-burning carry out multiple step format sintering in different temperature zones, can be one
Determine the progress for promoting the reaction in degree, is thus conducive to final product and forms stable phase structure and there is good electrification
Learn performance.
The method that the present invention uses the sintering of multiple step format prelithiation, the pre-burning certain time in low temperature segment limit, by presoma
It is removed in advance with the non-effective component such as the crystallization water contained by lithium salts, carbonate, hydroxyl.Mixture on the one hand can be improved in this way
Bulk density, promote material useful load in unit volume saggar, on the other hand can remove anion to oxidation in presoma
During object Morphological Transitions, part lithium ion is added in time and adulterates fluxing element, participates in synthetic reaction, forms preliminary layer
Shape structural framing promotes it preferably to the polynary stratiform thaumatropy of lithium nickel cobalt manganese, to improve stabilization of the material on crystal structure
Property.After completing pre-burning, thus remaining lithium salts and pre-burning material mixed sintering are easier to enter the layer structure preliminarily formed
It is interior, during lithium ion gradually reacts completely with presoma, realize it is more uniform bulk phase-doped, formed stable structure,
The anode material for lithium-ion batteries haveing excellent performance.
The method that above-mentioned prelithiation step sintering provided by the invention prepares positive electrode, it is steady to can not only obtain structure
It is fixed, the anode material for lithium-ion batteries of electrochemical performance, and simple process, production process is easily controllable, production cost
It is low, it is suitable for large-scale industrial production.
Compared with prior art, the present invention has an advantage that
(1) method of prelithiation step sintering is used, it is possible to reduce with lithium amount, reduce the consumption of lithium in production, drop simultaneously
The low residual lithium of positive electrode finished surface retains, and reduces negative effect of the residual lithium to battery quality and performance.
(2) technique for using prelithiation step sintering, can be during first sintering in removal presoma and lithium salts
Inert matter (crystallization water, hydroxyl, carbonate etc.), reduce mixture volume, increase in unit volume effectively material
Useful load promotes whole process production efficiency to improve unit production capacity.
(3) in a preferred embodiment, it using the technique of prelithiation step sintering, is added before low-temperature zone pre-burning starts
The doped chemical (helping to be sintered, the fusion of lithium source and presoma) of fluxing property, adds rock-steady structure type and mixes after pre-burning
Miscellaneous element (be conducive to doped chemical more uniformly, deeper into intracell, on the key temperatures point that layer structure is formed plus
Enter, better than addition at the very start), final sintering temperature can be reduced, energy loss is reduced.
Detailed description of the invention
Fig. 1 is to be compared using the button cell cycle performance figure of positive electrode production in embodiment 1 and comparative example 1.
Fig. 2 is to be compared using the button cell cycle performance figure of positive electrode production in embodiment 2 and comparative example 2.
Fig. 3 is to be compared using the button cell cycle performance figure of positive electrode production in embodiment 3 and comparative example 3.
Fig. 4 is to be compared using the button cell cycle performance figure of positive electrode production in embodiment 4 and comparative example 4.
Fig. 5 is 3 presoma nickel cobalt manganese composite hydroxide presoma Ni of embodiment0.62Co0.18Mn0.2(OH)2Scanning electron microscope
SEM photograph.
Fig. 6 is the scanning electron microscope sem photo for the material for (passing through step (2) pre-burning) after 3 low temperature presintering of embodiment.
Fig. 7 is 3 finished product of embodiment (by step (2) pre-burning and step (3) pre-burning) scanning of materials Electronic Speculum SEM photograph.
Fig. 8 is 3 finished-product material scanning electron microscope sem photo of comparative example.
Fig. 9 is 3 presoma of embodiment (nickel cobalt manganese composite hydroxide presoma Ni0.62Co0.18Mn0.2(OH)2), low temperature it is pre-
Sample after burning (passing through step (2) pre-burning), finished product (by step (2) pre-burning and step (3) pre-burning) and 2 finished product of comparative example
XRD composes comparison diagram entirely.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of method that prelithiation step sintering prepares anode material for lithium-ion batteries, this method include with
Lower step:
(1) according to the ratio of molar ratio 1:M, nickel presoma and lithium salts are weighed；
(2) nickel presoma is uniformly mixed with the lithium salts for accounting for total amount percentage X, is warming up to t1 DEG C of temperature, is sintered T1 hours；
(3) material after the completion of step (2) pre-burning is mixed with remainder (1-X) lithium salts, is warming up to t2 DEG C of temperature, sintering
T2 hours, after broken, screening, obtain positive electrode；
Wherein, t2 > t1.
The temperature difference of preferred embodiment in accordance with the present invention, preferably t2 and t1 is 150-700 DEG C, preferably 200-
600 DEG C, more preferably 300-500 DEG C.
Preferred embodiment in accordance with the present invention, preferably t1 range are 300 DEG C≤t1≤600 DEG C, preferably 400 DEG C≤t1
≤500℃。
Preferred embodiment in accordance with the present invention, preferably t2 range be 700 DEG C≤t2≤1200 DEG C, preferably 750 DEG C≤
t2≤950℃。
Preferred embodiment in accordance with the present invention, T1 range are 1h≤T1≤5h, preferably 2h≤T1≤3h.
Preferred embodiment in accordance with the present invention, T2 range are 4h≤T2≤14h, preferably 6h≤T2≤12h.
Preferred embodiment in accordance with the present invention, preferably X range be 10%≤X≤50%, preferably X range be 20%≤
X≤30%.
Preferred embodiment in accordance with the present invention, preferably M range are 1≤M≤1.25.
Preferred embodiment in accordance with the present invention, preferred steps (2) mix in the presence of doped chemical M ' compound,
In, preferably M ' is one or more elements of Sr, Ba, Na, La, Ce, F.
Preferred embodiment in accordance with the present invention, preferably M ' compound and the molar ratio of nickel presoma are 0.0001-
0.01:1。
Preferred embodiment in accordance with the present invention, preferred steps (3) mix in the presence of doped chemical M " compound,
In, preferably M " is one or more elements of Al, Mg, Zr, Ca, Ti, Si, Hf, Y, Nb.
The molar ratio of preferred embodiment in accordance with the present invention, M " compound and nickel presoma is 0.0001-0.01:1.
Preferred embodiment in accordance with the present invention, the nickel presoma are the compound hydrogen-oxygen of nickel cobalt manganese and/or nickel cobalt aluminium
Compound, the compound carbonate of nickel cobalt manganese and/or nickel cobalt aluminium, the compound acetate of nickel cobalt manganese and/or nickel cobalt aluminium, nickel cobalt manganese and/or
One of compound oxalates of nickel cobalt aluminium is a variety of.
Preferred embodiment in accordance with the present invention, the preferably described lithium salts are lithium carbonate, lithium hydroxide, lithium nitrate and chlorination
Lithium it is one or more.
Preferred embodiment in accordance with the present invention, prelithiation step sintering provided by the invention are preparing lithium ion battery just
The method of pole material, comprising the following steps:
(1) according to the ratio of molar ratio 1:M, nickel presoma and lithium salts are weighed respectively；
(2) by nickel presoma and account for total amount percentage X lithium salts and doped chemical M ' compound be uniformly mixed, be warming up to temperature
T1 DEG C of progress pre-burning is spent, is sintered T1 hours；
(3) material after the completion of step (2) pre-burning is mixed with remainder (1-X) lithium salts and doped chemical M " compound,
It is warming up to t2 DEG C of temperature, is sintered T2 hours, after broken, screening, obtains the positive electrode.
In above-mentioned preparation method, nickel presoma described in step (1) is nickel cobalt manganese or nickel cobalt aluminum complex hydroxide, nickel cobalt
One in manganese or nickel cobalt aluminium compound carbonate, nickel cobalt manganese or the compound acetate of nickel cobalt aluminium, nickel cobalt manganese or the compound oxalates of nickel cobalt aluminium
It plants or in which several；It is preferred that the lithium salts is lithium carbonate, lithium hydroxide, lithium nitrate, one kind of lithium chloride or in which several；
The M range is 1≤M≤1.25.
In above-mentioned preparation method, X range described in step (2) be 10%≤X≤50%, t1 range be 300 DEG C≤t1≤
600 DEG C, T1 range is 1h≤T1≤5h, and M ' is one or more of elements of Sr, Ba, Na, La, Ce, F.Further, X is preferred
Preferably 400~500 DEG C of 20%~30%, t1, T1 preferably 2~3h.
In above-mentioned preparation method, t2 range described in step (3) is 700 DEG C≤t2≤1200 DEG C, preferably 750 DEG C≤t2
≤950℃；T2 range is 4h≤T2≤14h, preferably 6h≤T2≤12h.
In above-mentioned preparation method, M " is one or more of elements of Al, Mg, Zr, Ca, Ti, Si, Hf, Y, Nb.
The method that above-mentioned prelithiation step sintering provided by the invention prepares positive electrode, it is steady to can not only obtain structure
It is fixed, the anode material for lithium-ion batteries of electrochemical performance, and simple process, production process is easily controllable, production cost
It is low, it is suitable for large-scale industrial production.
Compared with prior art, the present invention has an advantage that
(1) method of prelithiation step sintering is used, it is possible to reduce with lithium amount, reduce the consumption of lithium in production, drop simultaneously
The low residual lithium of positive electrode finished surface retains, and reduces negative effect of the residual lithium to battery quality and performance.
(2) technique for using prelithiation step sintering, can be during first sintering in removal presoma and lithium salts
Inert matter (crystallization water, hydroxyl, carbonate etc.), reduce mixture volume, increase in unit volume effectively material
Useful load promotes whole process production efficiency to improve unit production capacity.
(3) in a preferred embodiment, it using the technique of prelithiation step sintering, is added before low-temperature zone pre-burning starts
The doped chemical (helping to be sintered, the fusion of lithium source and presoma) of fluxing property, adds rock-steady structure type and mixes after pre-burning
Miscellaneous element (be conducive to doped chemical more uniformly, deeper into intracell, on the key temperatures point that layer structure is formed plus
Enter, better than addition at the very start), final sintering temperature can be reduced, energy loss is reduced.
The present invention provides the anode material for lithium-ion batteries that method according to the present invention obtains.
The present invention provides a kind of lithium ion cell positive, and the lithium ion cell positive contains lithium ion of the present invention
Cell positive material.
According to the present invention, positive manufacturing process is that the positive electrode that will be prepared is mixed to get with conductive agent, binder
Then slurry is coated on aluminium foil and obtains by slurry.
The present invention provides a kind of lithium ion battery, the lithium ion battery include anode and cathode, wherein it is described just extremely this
The invention lithium ion cell positive.
According to the present invention, cathode can be cathode commonly used in the art.The present invention to this without special requirement, herein
It does not repeat.
According to the present invention, the conventional method that the preparation of lithium ion battery is referred to this field carries out, and the present invention is to this nothing
Particular/special requirement.Such as lithium ion battery may include solid lithium ion battery and liquid lithium ionic cell, if it is liquid lithium ion
Battery then needs positive/negative plate and diaphragm battery core being prepared in the way of winding, battery core is then packed into battery case, dries
It is roasting, electrolyte is injected, welded seal obtains battery using chemical conversion, aging.
The production method that a kind of button cell is provided below only is exemplary illustration, the model being not intended to limit the present invention
It encloses, the positive electrode that following embodiment obtains prepares button cell by the following method:
Firstly, by positive electrode of the invention, acetylene black and polyvinylidene fluoride (PVDF) according to mass ratio 95%:
2.5%:2.5% is mixed, and is diameter with the pressure punch forming of 100MPa coated on aluminium foil and drying and processing is carried out
12mm, thick 120 μm of anode pole piece, are then put into 120 DEG C of drying 12h in vacuum drying box for anode pole piece.
Cathode is 17mm using diameter, with a thickness of the Li sheet metal of 1mm；The polyethylene porous that diaphragm uses with a thickness of 25 μm
Film；Electrolyte uses the LiPF6 of 1mol/L, the equivalent mixed liquor of ethylene carbonate (EC) and diethyl carbonate (DEC).
Anode pole piece, diaphragm, cathode pole piece and electrolyte are respectively less than to the Ar gas gloves of 5ppm in water content and oxygen content
2025 type button cells are assembled into case, using battery at this time as unactivated battery.
The performance evaluation of button cell about production is such as given a definition:
2h is placed after production button cell, after open-circuit voltage is stablized, the mode that the current density to anode is 0.1C charges
To blanking voltage 4.3V, then constant-voltage charge 30min, blanking voltage 3.0V is then discharged to same current density；By same
Mode carry out again 1 time, using battery at this time as active cell.
Cycle performance test is as follows: use active cell, with the current density of 1C 3.0~4.5V voltage range,
At a temperature of 45 DEG C, the high temperature capacity retention ratio of 80 investigation materials is recycled.
Embodiment 1
The ratio of 1.04:1 weighs lithium carbonate (Li in molar ratio2CO3), nickel cobalt manganese compound carbonate presoma
Ni0.5Co0.2Mn0.3CO3.20% lithium carbonate and whole presomas are uniformly mixed by the first stage, 500 DEG C of roastings in air atmosphere
Burn 2h, natural cooling cooling.Second stage will be sintered products therefrom the first stage and be uniformly mixed with remaining 80% lithium carbonate,
950 DEG C of roasting 10h in air atmosphere, natural cooling cooling obtain nickel-cobalt lithium manganate cathode material after broken, sieving
LiNi0.5Co0.2Mn0.3O2.Test the nickel-cobalt lithium manganate cathode material, surface residual Li2CO3Value 890ppm, LiOH value 560ppm.
Under 4.3V voltage, material discharge capacity (0.2C) 169.8mAh/g for the first time.With the current density of 1C in the voltage zone of 3.0~4.5V
Between, at a temperature of 45 DEG C, conservation rate 98.3% is recycled after circulation 80 times, 80 weeks.
Comparative example 1
The ratio of 1.04:1 weighs lithium carbonate (Li in molar ratio2CO3), nickel cobalt manganese compound carbonate presoma
Ni0.5Co0.2Mn0.3CO3.Disposably after mixing by all raw materials, 950 DEG C of roasting 12h in air atmosphere, natural cooling drop
Temperature obtains nickel-cobalt lithium manganate cathode material LiNi after broken, sieving0.5Co0.2Mn0.3O2.Test nickle cobalt lithium manganate anode
Material, surface residual Li2CO3Value 1380ppm, LiOH value 720ppm.Under 4.3V voltage, material discharge capacity (0.2C) for the first time
165.3mAh/g.Voltage range with the current density of 1C in 3.0~4.5V follows after circulation 80 times, 80 weeks at a temperature of 45 DEG C
Environmentally friendly holdup 96.1%.
Embodiment 2
The ratio of 1.03:1:0.003:0.001 weighs lithium hydroxide (LiOH), nickel cobalt manganese composite hydroxide in molar ratio
Presoma Ni0.85Co0.09Mn0.06(OH)2, silica (SiO2), cerium oxide (CeO2).First stage, by 30% hydroxide
Lithium and whole presomas, additive cerium oxide are uniformly mixed, 400 DEG C of roasting 3h in oxygen atmosphere, natural cooling cooling.Second-order
Section, will be sintered products therefrom the first stage and be uniformly mixed with remaining 70% lithium hydroxide, additive silica, oxygen atmosphere
In 750 DEG C of roasting 12h, natural cooling cooling obtains doping type nickel-cobalt lithium manganate cathode material LiNi after broken, sieving0.8 5Co0.09Mn0.06Si0.003Ce0.001O2.008.Test the nickel-cobalt lithium manganate cathode material, surface residual Li2CO3Value 3270ppm,
LiOH value 4350ppm.Under 4.3V voltage, material discharge capacity (0.2C) 199.8mAh/g for the first time.With the current density of 1C 3.0
The voltage range of~4.5V recycles conservation rate 95.7% after circulation 80 times, 80 weeks at a temperature of 45 DEG C.
Comparative example 2
The ratio of 1.03:1:0.003:0.001 weighs lithium hydroxide (LiOH), nickel cobalt manganese composite hydroxide in molar ratio
Presoma Ni0.85Co0.09Mn0.06(OH)2, silica (SiO2), cerium oxide (CeO2).All raw materials are disposably uniformly mixed
Afterwards, 750 DEG C of roasting 15h in oxygen atmosphere, natural cooling cooling obtain doping type nickle cobalt lithium manganate anode after broken, sieving
Material LiNi0.85Co0.09Mn0.06Si0.003Ce0.001O2.008.Test the nickel-cobalt lithium manganate cathode material, surface residual Li2CO3Value
5100ppm, LIOH value 6610ppm.Under 4.3V voltage, material discharge capacity (0.2C) 194.2mAh/g for the first time.With the electric current of 1C
Voltage range of the density in 3.0~4.5V recycles conservation rate 91.7% after circulation 80 times, 80 weeks at a temperature of 45 DEG C.
Embodiment 3
The ratio of 1.03:1:0.001:0.004 weighs lithium nitrate (LiNO in molar ratio3), nickel cobalt manganese composite hydroxide
Presoma Ni0.62Co0.18Mn0.2(OH)2, barium carbonate (BaCO3), zirconium dioxide (ZrO2).First stage, by 25% lithium nitrate
It is uniformly mixed with whole presomas, additive barium carbonate, 450 DEG C of roasting 3h in air atmosphere, natural cooling cooling.Second-order
Section, will be sintered products therefrom the first stage and be uniformly mixed with remaining 75% lithium nitrate, additive zirconium oxide, in air atmosphere
910 DEG C of roasting 8h, natural cooling cooling obtain doping type nickel-cobalt lithium manganate cathode material LiNi after broken, sieving0.62
Co0.18Mn0.2Zr0.004Ba0.001O2.009.Test the nickel-cobalt lithium manganate cathode material, surface residual Li2CO3Value 1510ppm, LiOH
Value 1430ppm.Under 4.3V voltage, material discharge capacity (0.2C) 176.6mAh/g for the first time.With the current density of 1C 3.0~
The voltage range of 4.5V recycles conservation rate 96.9% after circulation 80 times, 80 weeks at a temperature of 45 DEG C.
Comparative example 3
The ratio of 1.03:1:0.001:0.004 weighs lithium nitrate (LiNO in molar ratio3), nickel cobalt manganese composite hydroxide
Presoma Ni0.62Co0.18Mn0.2(OH)2, barium carbonate (BaCO3), zirconium dioxide (ZrO2).All raw materials are disposably uniformly mixed
Afterwards, 910 DEG C of roasting 11h in air atmosphere, natural cooling cooling obtain doping type nickle cobalt lithium manganate anode after broken, sieving
Material LiNi0.62Co0.18Mn0.2Zr0.004Ba0.001O2.009.Test the nickel-cobalt lithium manganate cathode material, surface residual Li2CO3Value
2040ppm, LiOH value 2210ppm.Under 4.3V voltage, material discharge capacity (0.2C) 172.3mAh/g for the first time.With the electric current of 1C
Voltage range of the density in 3.0~4.5V recycles conservation rate 93.4% after circulation 80 times, 80 weeks at a temperature of 45 DEG C.
Embodiment 4
The ratio of 1.05:1:0.003:0.001 weighs lithium hydroxide (LiOH), nickel cobalt aluminum complex hydroxide in molar ratio
Presoma Ni0.88Co0.09Al0.03(OH)2.03, titanium dioxide (TiO2), sodium fluoride (NaF).First stage, by 35% hydroxide
Lithium and whole presomas, additive sodium fluoride are uniformly mixed, 350 DEG C of roasting 1.5h in oxygen atmosphere, natural cooling cooling.Second
Stage will be sintered products therefrom the first stage and be uniformly mixed with remaining 70% lithium hydroxide, additive titanium dioxide, oxygen gas
730 DEG C of roasting 12.5h in atmosphere, natural cooling cooling obtain doping type nickel-cobalt lithium manganate cathode material Li after broken, sieving
Ni0.88Co0.09Al0.03Ti0.003Na0.001O2.006F0.001.Test the nickel cobalt lithium aluminate cathode material, surface residual Li2CO3Value
4610ppm, LIOH value 5100ppm.Under 4.3V voltage, material discharge capacity (0.2C) 207.2mAh/g for the first time.With the electric current of 1C
Voltage range of the density in 3.0~4.5V recycles conservation rate 94.8% after circulation 80 times, 80 weeks at a temperature of 45 DEG C.
Comparative example 4
The ratio of 1.03:1:0.003:0.001 weighs lithium hydroxide (LiOH), nickel cobalt aluminum complex hydroxide in molar ratio
Presoma Ni0.88Co0.09Al0.03(OH)2.03, titanium dioxide (TiO2), sodium fluoride (NaF).All raw materials are disposably mixed
After even, 730 DEG C of roasting 14h in oxygen atmosphere, natural cooling cooling is obtaining doping type nickel cobalt lithium aluminate just after broken, sieving
Pole material LiNi0.88Co0.09Al0.03Ti0.003Na0.001O2.006F0.001.Test the nickel-cobalt lithium manganate cathode material, surface residual
Li2CO3Value 7840ppm, LIOH value 8890ppm.Under 4.3V voltage, material discharge capacity (0.2C) 202.3mAh/g for the first time.With 1C
Current density 3.0~4.5V voltage range, at a temperature of 45 DEG C, circulation 80 times, 80 weeks after recycle conservation rate 90.5%.
The production of button cell, the positive electrode that embodiment and comparative example obtains prepare button electricity by the following method
Pond:
Firstly, by positive electrode, acetylene black and polyvinylidene fluoride (PVDF) according to mass ratio 95%:2.5%:2.5%
It is mixed, with the pressure punch forming of 100MPa is diameter 12mm, 120 μm thick coated on aluminium foil and drying and processing is carried out
Anode pole piece, anode pole piece is then put into 120 DEG C of drying 12h in vacuum drying box.
Cathode is 17mm using diameter, with a thickness of the Li sheet metal of 1mm；The polyethylene porous that diaphragm uses with a thickness of 25 μm
Film；Electrolyte uses the LiPF6 of 1mol/L, the equivalent mixed liquor of ethylene carbonate (EC) and diethyl carbonate (DEC).
Anode pole piece, diaphragm, cathode pole piece and electrolyte are respectively less than to the Ar gas gloves of 5ppm in water content and oxygen content
2025 type button cells are assembled into case, using battery at this time as unactivated battery.
The performance evaluation of button cell about production is such as given a definition:
2h is placed after production button cell, after open-circuit voltage is stablized, the mode that the current density to anode is 0.1C charges
To blanking voltage 4.3V, then constant-voltage charge 30min, blanking voltage 3.0V is then discharged to same current density；By same
Mode carry out again 1 time, using battery at this time as active cell.
Cycle performance test is as follows: use active cell, with the current density of 1C 3.0~4.5V voltage range,
At a temperature of 45 DEG C, the high temperature capacity retention ratio of 80 investigation materials is recycled.
In the present invention, surface residual Li2CO3Include the following steps: with LiOH test method
Using potentiometric titrimeter, the ultrapure water of 5.00 ± 0.02g+ of sample about (95.0 ± 0.5) g is added to 200ml's
In beaker, stirring and dissolving 5min is filtered, is tested.
In the present invention, XRD test method includes the following steps:
Material is added in glass sample frame, presses and scrape flat surface, completes sample preparation.X-ray diffractometer is opened, by what is made
Sample is placed in test specimens sample platform, is selected 10 ° of -80 ° of angular ranges, is tested.
Fig. 1 is to be compared using the button cell cycle performance figure of positive electrode production in embodiment 1 and comparative example 1.
Fig. 2 is to be compared using the button cell cycle performance figure of positive electrode production in embodiment 2 and comparative example 2.
Fig. 3 is to be compared using the button cell cycle performance figure of positive electrode production in embodiment 3 and comparative example 3.
Fig. 4 is to be compared using the button cell cycle performance figure of positive electrode production in embodiment 4 and comparative example 4.
Fig. 5 is 3 presoma nickel cobalt manganese composite hydroxide presoma Ni of embodiment0.62Co0.18Mn0.2(OH)2Scanning electron microscope
SEM photograph.
Fig. 6 is the scanning electron microscope sem photo for the material for (passing through step (2) pre-burning) after 3 low temperature presintering of embodiment.
Fig. 7 is 3 finished product of embodiment (by step (2) pre-burning and step (3) pre-burning) scanning of materials Electronic Speculum SEM photograph.
Fig. 8 is 3 finished-product material scanning electron microscope sem photo of comparative example.
Fig. 9 is 3 presoma of embodiment (nickel cobalt manganese composite hydroxide presoma Ni0.62Co0.18Mn0.2(OH)2), low temperature it is pre-
Sample after burning (passing through step (2) pre-burning), finished product (by step (2) pre-burning and step (3) pre-burning) and 2 finished product of comparative example
XRD composes comparison diagram entirely.
It can be seen that prelithiation sintering process sample compared to the once sintered sample of tradition, In by the result of Fig. 1 to Fig. 4
Under the conditions of same test, there is better cycle performance.
It is not yet built completely by the layered crystal structure that the result of Fig. 5 to Fig. 9 can be seen that low temperature presintering phase material
It is vertical, secondary high-temperature doping roasting is carried out in this node, finished product primary particle after high temperature sintering can be made to grow complete, mutual structure
It is form compact and stable, there is better crystallization degree and apparent form than once sintered sample.
Table 1 is the discharge capacity and remnants Li of embodiment 1,2,3,4 and comparative example 1,2,3,42CO3, LiOH data.
Table 1
| Discharge capacity (0.2C) for the first time | Remaining Li2CO3(ppm) | Remaining LiOH (ppm) | |
| Embodiment 1 | 169.8 | 890 | 560 |
| Comparative example 1 | 165.3 | 1380 | 720 |
| Embodiment 2 | 199.8 | 3270 | 4350 |
| Comparative example 2 | 194.2 | 5100 | 6610 |
| Embodiment 3 | 176.6 | 1510 | 1430 |
| Comparative example 3 | 172.3 | 2040 | 2210 |
| Embodiment 4 | 207.2 | 4610 | 5100 |
| Comparative example 4 | 202.3 | 7840 | 8890 |
As can be seen from Table 1 under identical element Comparative, prelithiation sintering process sample remnants Li2CO3More with LiOH
It is low, while discharge capacity is higher for the first time, properties of product are more excellent.
By the comparison discovery to different sintering processing embodiments and comparative example, by the way of prelithiation step sintering,
Calcining time can be shortened to a certain extent, reduce sintering temperature, the positive electrode made has more stable structure, more
High specific capacity and better cycle performance.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (10)
1. a kind of method that prelithiation step sintering prepares anode material for lithium-ion batteries, which is characterized in that this method include with
Lower step:
(1) according to the ratio of molar ratio 1:M, nickel presoma and lithium salts are weighed；
(2) nickel presoma is uniformly mixed with the lithium salts for accounting for total amount percentage X, is warming up to t1 DEG C of temperature, is sintered T1 hours；
(3) material after the completion of step (2) pre-burning is mixed with remainder (1-X) lithium salts, is warming up to t2 DEG C of temperature, sintering T2 is small
When, after broken, screening, obtain positive electrode；
Wherein, t2 > t1.
2. according to the method described in claim 1, wherein, the temperature difference of t2 and t1 are 150-700 DEG C, preferably 200-600 DEG C,
More preferably 300-500 DEG C.
3. method according to claim 1 or 2, wherein
T1 range is 300 DEG C≤t1≤600 DEG C, preferably 400 DEG C≤t1≤500 DEG C；And/or
T2 range is 700 DEG C≤t2≤1200 DEG C, preferably 750 DEG C≤t2≤950 DEG C.
4. method described in any one of -3 according to claim 1, wherein
T1 range is 1h≤T1≤5h, preferably 2h≤T1≤3h；And/or
T2 range is 4h≤T2≤14h, preferably 6h≤T2≤12h.
5. method described in any one of -4 according to claim 1, wherein
X range is 10%≤X≤50%, and preferably X range is 20%≤X≤30%；And/or
M range is 1≤M≤1.25.
6. method described in any one of -5 according to claim 1, wherein
Step (2) mixes in the presence of doped chemical M ' compound, wherein M ' is the one or more of Sr, Ba, Na, La, Ce, F
The molar ratio of element, M ' compound and nickel presoma is 0.0001-0.01:1；And/or
Step (3) mixes in the presence of doped chemical M " compound, wherein M " is Al, Mg, Zr, Ca, Ti, Si, Hf, Y, Nb
The molar ratio of one or more elements, M " compound and nickel presoma is 0.0001-0.01:1.
7. method described in any one of -6 according to claim 1, wherein
The nickel presoma is the compound carbonic acid of the complex hydroxide of nickel cobalt manganese and/or nickel cobalt aluminium, nickel cobalt manganese and/or nickel cobalt aluminium
Salt, the compound acetate of nickel cobalt manganese and/or nickel cobalt aluminium, nickel cobalt manganese and/or nickel cobalt aluminium one of compound oxalates or a variety of；
And/or
The lithium salts is the one or more of lithium carbonate, lithium hydroxide, lithium nitrate and lithium chloride.
8. the anode material for lithium-ion batteries that method described in any one of claim 1-7 obtains.
9. a kind of lithium ion cell positive, which is characterized in that the lithium ion cell positive contain lithium according to any one of claims 8 from
Sub- cell positive material.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes anode and cathode, wherein described just extremely to weigh
Benefit require 9 described in lithium ion cell positive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2019105527729 | 2019-06-25 | ||
| CN201910552772 | 2019-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110422890A true CN110422890A (en) | 2019-11-08 |
Family
ID=68410241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910596554.5A Pending CN110422890A (en) | 2019-06-25 | 2019-07-03 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion cell positive and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110422890A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082029A (en) * | 2019-12-31 | 2020-04-28 | 北京当升材料科技股份有限公司 | Lithium-rich manganese-based material and preparation method and application thereof |
| CN111370682A (en) * | 2020-03-26 | 2020-07-03 | 四川青源新材料有限公司 | Lithium ion battery anode material precursor, anode material and preparation method |
| CN111640932A (en) * | 2020-06-03 | 2020-09-08 | 深圳市研一新材料有限责任公司 | High-purity positive electrode lithium supplement additive, preparation method thereof and lithium ion battery |
| CN112993239A (en) * | 2019-12-17 | 2021-06-18 | 天津国安盟固利新材料科技股份有限公司 | High-pressure-resistant low-cobalt ternary cathode material and preparation method thereof |
| CN113184923A (en) * | 2021-04-29 | 2021-07-30 | 昆山宝创新能源科技有限公司 | Preparation method of niobium modified lithium-rich manganese-based material, positive electrode material and lithium ion battery |
| CN113683122A (en) * | 2021-08-19 | 2021-11-23 | 蜂巢能源科技有限公司 | Iron-manganese-based positive electrode material, and preparation method and application thereof |
| CN113735193A (en) * | 2021-01-05 | 2021-12-03 | 厦门厦钨新能源材料股份有限公司 | High-capacity lithium ion battery |
| CN114497452A (en) * | 2021-12-28 | 2022-05-13 | 高点(深圳)科技有限公司 | Positive electrode material for silicon battery and preparation method and application thereof |
| CN114613989A (en) * | 2022-04-01 | 2022-06-10 | 湖南桑瑞新材料有限公司 | Preparation method of single-crystal ternary cathode material of lithium ion battery, cathode material and lithium ion battery |
| CN115974172A (en) * | 2022-09-29 | 2023-04-18 | 宁夏汉尧富锂科技有限责任公司 | Method for preparing low-cobalt and cobalt-free cathode material by pre-sintering lithium-deficient process and application of low-cobalt and cobalt-free cathode material |
| WO2023115289A1 (en) * | 2021-12-21 | 2023-06-29 | 昶联金属材料应用制品(广州)有限公司 | Nickel-rich material and preparation method therefor, positive electrode plate, battery and electric equipment |
| EP4091990A4 (en) * | 2020-06-15 | 2023-08-16 | Lg Chem, Ltd. | Method for preparing positive electrode active material |
| US12126019B2 (en) | 2020-06-15 | 2024-10-22 | Lg Chem, Ltd. | Method of preparing positive electrode active material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070191A (en) * | 2006-05-08 | 2007-11-14 | 上海川那电池制造有限公司 | Process for preparing lithium ion cell positive pole material |
| CN101117234A (en) * | 2006-08-04 | 2008-02-06 | 比亚迪股份有限公司 | Method for preparing doping lithium-enriching spinelle lithium manganese oxide |
| CN101355159A (en) * | 2008-09-17 | 2009-01-28 | 金瑞新材料科技股份有限公司 | Method for preparing lithium ion battery anode material nickle cobalt lithium manganate |
| CN103232069A (en) * | 2013-03-20 | 2013-08-07 | 江苏凯力克钴业股份有限公司 | Lithium ion battery lithium-rich manganese base positive electrode material preparation method |
| WO2016082426A1 (en) * | 2014-11-24 | 2016-06-02 | Beijing Institute Of Technology | Lithium-rich manganese-based cathode material, its preparation method and lithium-ion battery |
| CN107681128A (en) * | 2017-08-14 | 2018-02-09 | 北大先行科技产业有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN109286017A (en) * | 2018-11-08 | 2019-01-29 | 桑德集团有限公司 | The preparation method and high-tap density lithium-rich manganese-based anode material and lithium ion battery of high-tap density lithium-rich manganese-based anode material |
| CN109461925A (en) * | 2018-06-29 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of monocrystalline nickel-cobalt lithium manganate cathode material, presoma and preparation method thereof |
| CN109728262A (en) * | 2018-11-30 | 2019-05-07 | 高点(深圳)科技有限公司 | Anode material for lithium-ion batteries and its preparation method and application |
-
2019
- 2019-07-03 CN CN201910596554.5A patent/CN110422890A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070191A (en) * | 2006-05-08 | 2007-11-14 | 上海川那电池制造有限公司 | Process for preparing lithium ion cell positive pole material |
| CN101117234A (en) * | 2006-08-04 | 2008-02-06 | 比亚迪股份有限公司 | Method for preparing doping lithium-enriching spinelle lithium manganese oxide |
| CN101355159A (en) * | 2008-09-17 | 2009-01-28 | 金瑞新材料科技股份有限公司 | Method for preparing lithium ion battery anode material nickle cobalt lithium manganate |
| CN103232069A (en) * | 2013-03-20 | 2013-08-07 | 江苏凯力克钴业股份有限公司 | Lithium ion battery lithium-rich manganese base positive electrode material preparation method |
| WO2016082426A1 (en) * | 2014-11-24 | 2016-06-02 | Beijing Institute Of Technology | Lithium-rich manganese-based cathode material, its preparation method and lithium-ion battery |
| CN107681128A (en) * | 2017-08-14 | 2018-02-09 | 北大先行科技产业有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN109461925A (en) * | 2018-06-29 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of monocrystalline nickel-cobalt lithium manganate cathode material, presoma and preparation method thereof |
| CN109286017A (en) * | 2018-11-08 | 2019-01-29 | 桑德集团有限公司 | The preparation method and high-tap density lithium-rich manganese-based anode material and lithium ion battery of high-tap density lithium-rich manganese-based anode material |
| CN109728262A (en) * | 2018-11-30 | 2019-05-07 | 高点(深圳)科技有限公司 | Anode material for lithium-ion batteries and its preparation method and application |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112993239A (en) * | 2019-12-17 | 2021-06-18 | 天津国安盟固利新材料科技股份有限公司 | High-pressure-resistant low-cobalt ternary cathode material and preparation method thereof |
| WO2021136490A1 (en) * | 2019-12-31 | 2021-07-08 | 北京当升材料科技股份有限公司 | Lithium-rich manganese-based material, preparation method therefor and application thereof |
| CN111082029B (en) * | 2019-12-31 | 2021-08-03 | 北京当升材料科技股份有限公司 | Lithium-rich manganese-based material and preparation method and application thereof |
| CN111082029A (en) * | 2019-12-31 | 2020-04-28 | 北京当升材料科技股份有限公司 | Lithium-rich manganese-based material and preparation method and application thereof |
| CN111370682A (en) * | 2020-03-26 | 2020-07-03 | 四川青源新材料有限公司 | Lithium ion battery anode material precursor, anode material and preparation method |
| CN111640932B (en) * | 2020-06-03 | 2022-05-13 | 无锡零一未来新材料技术研究院有限公司 | High-purity positive electrode lithium supplement additive, preparation method thereof and lithium ion battery |
| CN111640932A (en) * | 2020-06-03 | 2020-09-08 | 深圳市研一新材料有限责任公司 | High-purity positive electrode lithium supplement additive, preparation method thereof and lithium ion battery |
| US12126019B2 (en) | 2020-06-15 | 2024-10-22 | Lg Chem, Ltd. | Method of preparing positive electrode active material |
| EP4091990A4 (en) * | 2020-06-15 | 2023-08-16 | Lg Chem, Ltd. | Method for preparing positive electrode active material |
| CN113735193A (en) * | 2021-01-05 | 2021-12-03 | 厦门厦钨新能源材料股份有限公司 | High-capacity lithium ion battery |
| CN113735193B (en) * | 2021-01-05 | 2023-02-10 | 厦门厦钨新能源材料股份有限公司 | High-capacity lithium ion battery |
| CN113184923A (en) * | 2021-04-29 | 2021-07-30 | 昆山宝创新能源科技有限公司 | Preparation method of niobium modified lithium-rich manganese-based material, positive electrode material and lithium ion battery |
| CN113683122B (en) * | 2021-08-19 | 2022-12-09 | 蜂巢能源科技有限公司 | Iron-manganese-based positive electrode material, and preparation method and application thereof |
| CN113683122A (en) * | 2021-08-19 | 2021-11-23 | 蜂巢能源科技有限公司 | Iron-manganese-based positive electrode material, and preparation method and application thereof |
| WO2023115289A1 (en) * | 2021-12-21 | 2023-06-29 | 昶联金属材料应用制品(广州)有限公司 | Nickel-rich material and preparation method therefor, positive electrode plate, battery and electric equipment |
| CN114497452A (en) * | 2021-12-28 | 2022-05-13 | 高点(深圳)科技有限公司 | Positive electrode material for silicon battery and preparation method and application thereof |
| CN114613989A (en) * | 2022-04-01 | 2022-06-10 | 湖南桑瑞新材料有限公司 | Preparation method of single-crystal ternary cathode material of lithium ion battery, cathode material and lithium ion battery |
| CN115974172A (en) * | 2022-09-29 | 2023-04-18 | 宁夏汉尧富锂科技有限责任公司 | Method for preparing low-cobalt and cobalt-free cathode material by pre-sintering lithium-deficient process and application of low-cobalt and cobalt-free cathode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110422890A (en) | Anode material for lithium-ion batteries and preparation method thereof and lithium ion cell positive and lithium ion battery | |
| US20240162420A1 (en) | Layered cobalt-free positive electrode material and preparation method therefor, and lithium-ion battery | |
| CN109336193B (en) | Multi-element in-situ co-doped ternary material precursor and preparation method and application thereof | |
| WO2022170648A1 (en) | High-entropy positive electrode material, and preparation method therefor and application thereof | |
| CN107302087B (en) | A kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and preparation method thereof | |
| CN109192972A (en) | Mixture of multi-elements is mixed with modified tertiary cathode material and preparation method thereof | |
| CN102208611B (en) | A kind of induced crystallization synthetic method of lithium ion secondary battery positive electrode dusty material | |
| CN109437339A (en) | Nickelic quaternary positive electrode material precursor and nickelic quaternary positive electrode, preparation method and purposes | |
| CN109216688A (en) | A kind of ternary lithium electric material, preparation method and lithium ion battery | |
| CN110380024A (en) | Sodium transition metal oxide with P3 structure, preparation method thereof and sodium ion battery | |
| CN109167056A (en) | Tungsten ion doped high-nickel layered oxide lithium battery positive electrode material and preparation method thereof | |
| CN106910882A (en) | A kind of lithium ion battery preparation method of large single crystal layered cathode material | |
| CN102891304B (en) | Lithium titanate and lithium ion battery using lithium titanate negative electrode active material | |
| JP3263082B2 (en) | Low-temperature synthesis of layered lithiated transition metal oxides | |
| CN109449438A (en) | Quaternary positive electrode, preparation method and purposes | |
| CN109585845A (en) | NCM-NCMA positive electrode, preparation method and purposes | |
| CN103606663B (en) | A kind of Multiplying-power lithium-rich composite anode material and preparation method thereof | |
| CN106299320A (en) | Modified nickel cobalt lithium manganate ternary material and preparation method thereof | |
| CN103137963B (en) | A kind of lithium-rich manganese-based anode material and preparation method thereof | |
| CN109256557A (en) | Nickelic layered oxide lithium electricity positive electrode of a kind of perofskite type oxide cladding and preparation method thereof | |
| CN109686969A (en) | A kind of sodium-ion battery of the preparation and application of stratiform transition metal oxide the material material | |
| CN115513449A (en) | Layered lithium-rich manganese-based high-entropy cathode material, preparation method thereof and battery | |
| CN109585846A (en) | Ternary core-quaternary shell positive electrode, preparation method and purposes | |
| CN109088067A (en) | A kind of preparation method of low cobalt doped spinel-layer structure nickel ion doped two-phase composite positive pole | |
| CN101609893A (en) | Lithium ion secondary battery anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191108 |
|
| RJ01 | Rejection of invention patent application after publication |