CN105742595A - Nickel-containing lithium-rich and manganese-based positive electrode material and preparation method thereof, positive electrode and battery - Google Patents
Nickel-containing lithium-rich and manganese-based positive electrode material and preparation method thereof, positive electrode and battery Download PDFInfo
- Publication number
- CN105742595A CN105742595A CN201610123666.5A CN201610123666A CN105742595A CN 105742595 A CN105742595 A CN 105742595A CN 201610123666 A CN201610123666 A CN 201610123666A CN 105742595 A CN105742595 A CN 105742595A
- Authority
- CN
- China
- Prior art keywords
- lithium
- source
- nickel
- manganese
- positive electrode
- 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
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of materials for lithium-ion batteries, and discloses a nickel-containing lithium-rich and manganese-based positive electrode material and a preparation method thereof. The method specifically comprises the following steps: preparing a solution from a nickel source, a manganese source, a doping element source, a complexing agent, a strong oxidant and a precipitator with a solvent; mixing the nickel source, the manganese source and the doping element source and adding the complexing agent under a stirring condition to obtain a complexing agent sediment; adding a strong oxidant solution and a precipitator solution to the complexing agent sediment under the stirring condition, and controlling the pH value of a system with aqueous ammonia until complete precipitation to obtain an intermediate sediment; and filtering, washing and drying the intermediate sediment and then mixing the sediment with the lithium source, and burning the mixture to obtain the nickel-containing lithium-rich and manganese-based positive electrode material. The invention further discloses a positive electrode and a battery prepared from the positive electrode material. According to the method disclosed by the invention, nickel elements in positive electrode material particles and on the surfaces thereof are fully oxidized, so that the uniformity and the stability of the positive electrode material are improved; and the cycling stability and the rate capability of the battery are improved.
Description
Technical field
The invention belongs to field of lithium ion battery material, be specifically related to a kind of nickeliferous lithium-rich manganese-based anode material and preparation method thereof, further relate to the Anode and battery made with this positive electrode.
Background technology
Along with electronics and IT products are more and more lighter, thin and microminiaturized, simultaneously along with the expanding day of the dynamical system battery requirements such as new-energy automobile, energy density that nowadays conventional lithium ion cell anode material lithium cobaltate, LiMn2O4, LiFePO 4 and nickel-cobalt-manganese ternary material can reach is more aobvious cannot meet practical application needs.And lithium-rich manganese base material can realize 250mAhg after modified-1Above capacity, higher than above-mentioned tradition positive electrode in any.
Nickeliferous lithium-rich manganese base material is current most study, the most rich lithium material of application prospect, this material is similar with positive electrodes such as known nickle cobalt lithium manganates, within the specific limits, along with the increase of nickel content in material component, the actual gram volume of material will increase, but, along with the increase of the introducing of Ni element and amount, will appear from the Ni ion phenomenon with Li ion mixing on the one hand, Ni ion occupies Li ion position, blocks Li ionic transport passages, thus reducing the cyclical stability of material；Ni ion will gather at material surface on the other hand, form one layer of rich nickel dam at material surface, directly result in material inefficiency first, the bad phenomenon such as high rate performance is poor.And the mixing of Ni ion and surface enrichment phenomenon are mostly derived from traditional material preparation process, Ni2+Aoxidize under oxygen atmosphere when the oxidation of ion sinters mainly by material, due to the deficiency etc. of the deficiency of oxygen atmosphere and sintering process, Ni2+Be difficult to homogeneous, be oxidized to Ni fully3+Ion.Thus limiting preparation and the application thereof of high-nickel material, therefore finding a kind of simple raising nickel element being effectively easily achieved again large-scale production at nickeliferous positive electrode, particularly the method for nickel-rich positive pole material homogeneity seems and important.
Solution to the problems described above relatively conventional at present is that to prepare lithium ion battery by the method for high-temperature calcination under high-load oxygen atmosphere environment nickeliferous, particularly nickelic positive electrode, but such method not only working condition is harsh, production cost is high, and cannot comparatively thoroughly solve the problems referred to above.Recently the technology adopting strong oxidizer oxidation nickelous element is also had to occur, as Chinese patent CN104201378A discloses a kind of method preparing the nickelic tertiary cathode material of lithium ion battery, oxidant is mixed by the method with ternary material precursor powder, then under oxygen containing atmosphere, calcining obtains required product, and the relatively general traditional method products obtained therefrom of products obtained therefrom has certain lifting.
But above-mentioned patented method there is also many deficiencies: first, the method directly by oxidant with precursor powder mixed calcining, introduce new impurity, while reducing materials processing performance, also increase washing cost when removing impurity.As described in method containing sodium, containing oxidants such as potassium, the alkali residual volume of material will be greatly improved, be unfavorable for the actual processed and applied of material；The application of the oxidants such as described slightly solubility bichromate, washing times when adding sintered product decontamination and production cost.Secondly, adopt strong oxidizer to mix with material precursor powder, belong to the catalytic oxidation process of pressed powder, there is a progressively diffusible oxydation process from outward appearance to inner essence, it is difficult to ensure that the Ni element within material granule also can be fully oxidized.Finally, finally sintering atmosphere and be still oxygen atmosphere when preparing product in this patented method, only in a slight decrease by oxygen purity aspect, and could not really realize air atmosphere calcining, cost reduces limitation.
And for example Chinese patent CN105047905A discloses the surface modifying method of a kind of nickel-rich positive pole material, and the method adopts the strong oxidizer Ni to rich nickel material surface2+Carry out a degree of oxidation to improve.Although the lifting of material property is served certain effect, but the method is only that the nickel to material surface enrichment has carried out partial oxidation on the one hand, it is difficult to be fully achieved whole oxidation, also only rests on material surface modifying simultaneously, to the internal Ni existed of material granule structure profound level2+But the efficient oxidation cannot be realized；Method described in this patent is that the high-nickel material to finished product is modified on the other hand, the courses of processing such as carrying out double sintering of still needing, and is also unfavorable for manufacturing the reduction of production cost.
Therefore exploitation is a kind of effectively reduces lithium ion anode material surface Ni2+Method, seemed particularly necessary.
Summary of the invention
It is an object of the invention to provide a kind of nickeliferous lithium-rich manganese-based anode material with homogeneity and stability.
The preparation method that it is a further object of the present invention to provide this positive electrode.
It is a further object of the present invention to provide the positive pole of a kind of battery.
It is a further object of the present invention to provide a kind of battery.
For reaching one of above-mentioned purpose, the present invention by the following technical solutions:
The preparation method of a kind of nickeliferous lithium-rich manganese-based anode material, comprises the following steps:
S1, nickel source, manganese source, doped chemical source, chelating agent, strong oxidizer, precipitant solvent are configured to solution；
S2, by nickel source, manganese source and doped chemical source solution mix, under stirring condition add chelating agent, obtain complex compound sediment；
Under S3, stirring condition, strong oxidant solution and precipitant solution are added complex compound sediment, and with the pH value of ammonia control system, until precipitation completely, obtains intermediate precipitation；
S4, intermediate precipitation is filtered, washing and dry, then mix with lithium source, after calcining, obtains nickeliferous lithium-rich manganese-based anode material.
Further, the formula of described nickeliferous lithium-rich manganese-based anode material is LixNiyMnzMwO2, wherein: 1≤x≤4/3,0≤y≤1,2/3≤z≤1, w=1-y-z, doped chemical M is at least one in Co, Al, Cr, Fe, Ti, V, Mg, Zn, Cu, Mo, Zr.
Further, described nickel source is NiSO4、NiSO4·6H2O、NiSO4·7H2O, Ni(NO3)2, Ni(NO3)2·6H2O、NiCl2And NiCl2·6H2At least one in O.Most preferred nickel source is Ni(NO3)2·6H2O。
Further, described manganese source is MnSO4、MnSO4·4H2O, Mn(NO3)2·4H2O、MnCl2、MnCl2·2H2O、MnCl2·4H2O、MnCl3、K2MnO4And KMnO4In at least one.Most preferred manganese source is MnSO4·4H2O。
Further, described doped chemical source is at least one in the sulfate of doped chemical M, nitrate, chloride, oxide；Doped chemical M is at least one in Co, Al, Cr, Fe, Ti, V, Mg, Zn, Cu, Mo, Zr.Most preferred doped chemical is Co；Cobalt source is CoSO4、CoSO4·7H2O, Co(NO3)2·6H2O、CoCl2·6H2At least one in O；Most preferred doped chemical source is Co(NO3)2·6H2O。
Further, described chelating agent is at least one in ammonia, oxalic acid, citric acid, tartaric acid, sulfosalicylic acid, orthophenanthroline, dimercaptopropanol, BAL, Unithiol, mercaptoethylmaine, TGA, thiourea, oxine, triethanolamine, EDTA, EGTA, ethylenediamine tetrapropionic acid and triethylenetetramine.Most preferred chelating agent is ammonia.
EGTA is ethylene glycol bis aminoethyl ether tetraacethyl.
Further, described strong oxidizer is at least one in peroxide, bichromate, permanganate.
Peroxide is the compound containing peroxy-O-O-, for instance persulfate (Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate etc.), hydrogen peroxide, sodium peroxide, peroxy acid；Bichromate is potassium dichromate such as；Permanganate is potassium permanganate such as.
Most preferred strong oxidizer is Ammonium persulfate..
Further, described precipitant is at least one in sodium hydroxide, potassium hydroxide, carbonate and bicarbonate.Most preferred precipitant is sodium hydroxide.
Further, described solvent is at least one in water, methanol, ethanol, propanol and ether.Most preferred solvent is water.
Further, described lithium source is at least one in lithium carbonate, Lithium hydrate, lithium acetate and lithium fluoride.
Further, the mass ratio in described step S4 intermediate precipitation and lithium source is 1:0.5 ~ 2.
Further, the concentration of described step S1 solution is 0.5 ~ 5mol L-1。
Further, the mixing speed of described step S2 is 50 ~ 900rpm, adopts mechanical agitation dispersion.
Further, the mixing speed of described step S3 is 50 ~ 900rpm, it is preferable that 600rpm.
Further, described step S3 carries out at 20 ~ 90 DEG C, it is preferable that 50 DEG C.
Further, the pH value of described step S3 controls is 10 ~ 12, it is preferable that 10.5 ~ 11.5.
Further, described step S4 dries as natural drying, vacuum drying or spray drying.
Further, described step S4 dries is 80 ~ 120 DEG C of vacuum drying 5 ~ 24h.
Further, described step S4 calcining is calcining 3～24h in 300～1000 DEG C of oxygen-containing atmospheres.
Further, described step S4 calcining is calcining 5～16h in 400～1000 DEG C of air atmospheres.
A kind of nickeliferous lithium-rich manganese-based anode material, is be prepared from by foregoing preparation method.
The positive pole of a kind of battery, including foregoing nickeliferous lithium-rich manganese-based anode material.
A kind of battery, including positive pole, negative pole, barrier film and electrolyte, described positive pole includes foregoing nickeliferous lithium-rich manganese-based anode material.
The method have the advantages that
The present invention is directed to positive electrode nickel element in preparation process to be difficult to complete oxidation and cause cation mixing and surface nickel enrichment, thus causing material conductivity and the problem of cyclical stability difference, have employed original position Autoxidation Method, utilize strong oxidizer, before nickel element does not form corresponding precipitation in positive electrode preparation process, just it is oxidized to Ni completely3+, making internal and surface the nickel element of positive electrode granule all be substantially oxidized, thus improving uniformity and the stability of positive electrode, and then improving cyclical stability and the high rate performance of battery.
Adopting nickeliferous lithium-rich manganese-based anode material prepared by the inventive method to have nickel distribution evenly than nickel-rich positive pole material prepared by existing method, without nickel surface enrichment phenomenon, crystal structure is intact, and the inside and outside nickel element of positive electrode is all fully oxidized to nickelic；The method is simple, condition is easy to control simultaneously; only need once sintered, and prior art is the tertiary cathode material to finished product is modified, the courses of processing such as carrying out double sintering of still needing; therefore the present invention is more convenient for large-scale production, can be substantially reduced manufacture of materials cost；After positive electrode circulates 115 weeks, capacity remains the 90.69% of initial capacity, and positive electrode prepared by existing method capacity after circulating 115 weeks only keeps 75.15%, far below the positive electrode of the present invention.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the nickel-rich positive pole material of comparative example；
Fig. 2 is the nickel element scattergram of the nickel-rich positive pole material of comparative example；
Fig. 3 is the SEM figure of the nickeliferous lithium-rich manganese-based anode material of embodiment 1；
Fig. 4 is the nickel element scattergram of the nickeliferous lithium-rich manganese-based anode material of embodiment 1；
Fig. 5 is the XRD figure of the nickeliferous lithium-rich manganese-based anode material of embodiment 1；
Fig. 6 is the cycle performance curve chart of the battery of embodiment 7.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further:
Comparative example
(1) K of 0.05g is weighed2Cr2O7It is dissolved in 10g water, and is stirred continuously, be subsequently adding 5g positive electrode LiNi0.5Co0.2Mn0.3O2, stirring obtains composite material；Then composite material is placed under 80 DEG C of conditions and dries 4h, it is thus achieved that dry composite material；
(2) the dry composite material that step 1) obtains is placed in air, is warming up to 400 DEG C and is sintered, and heat preservation sintering 4h, it is thus achieved that intermediate product；
(3) by step 2) intermediate product that obtains is dissolved in the water stirring, vacuum filtration, and wash and be placed under 100 DEG C of conditions dry 3h, prepared precursor product；
(4) precursor product that step 3) prepares is cooled down in atmosphere, grinds so that material reaches the particle size of regulation, namely obtains the nickel-rich positive pole material modifiied.
The SEM of this nickel-rich positive pole material as it is shown in figure 1, nickel element scattergram as shown in Figure 2.
In following example, nickel source, manganese source, chelating agent, strong oxidizer, precipitant consumption can adjust according to actual needs, as long as meeting the composition (Li of positive electrodexNiyMnzMwO2, 1≤x≤4/3,0≤y≤1,2/3≤z≤1, w=1-y-z, M is at least one in Co, Al, Cr, Fe, Ti, V, Mg, Zn, Cu, Mo, Zr).
Embodiment 1
(1) by 3.1691gMnSO4·4H2O, 1.8174gNi(NO3)2·6H2O and 0.1724gCoSO4·7H2O is dissolved in respectively in deionized water and makes 1mol L-1Solution, 7gNaOH and 5.7062g(NH4)2S2O8It is dissolved in respectively in deionized water and is configured to 2mol L-1Solution；
(2) being mixed in 250mL flask by manganese sulfate, nickel nitrate, cobalt sulfate solution, 50 DEG C of oil bath heating, 900rpm stirs, and adds 22.5mL ammonia, obtains complex compound sediment；
(3) 50 DEG C, sodium hydroxide solution and ammonium persulfate solution are added drop-wise to complex compound sediment respectively under 900rpm mechanical agitation, and control the pH value of system between 10.50 ~ 11.00 with ammonia, keep 50 DEG C, the continuously stirred 12h of 900rpm, under 50 DEG C of environment, stand 2h, obtain intermediate precipitation；
(4) gained intermediate precipitation being filtered, wash 2 times, at 105 DEG C of vacuum drying 8h, gained intermediate product weight 1.8904g, then with 1.4528gLi2CO3Mix homogeneously, is placed in air atmosphere 450 DEG C calcining 4h, and 900 DEG C of calcining 10h obtain the nickeliferous lithium-rich manganese-based anode material of 2.4271g.Its SEM as it is shown on figure 3, nickel element scattergram as shown in Figure 4, XRD figure is as shown in Figure 5.
Through contrast it can be seen that internal and surface the nickel element of the positive electrode granule of embodiment 1 is all substantially oxidized, nickel is more evenly distributed, and without nickel surface enrichment phenomenon, crystal structure is intact；And the nickel of positive pole material surface enrichment has only been carried out partial oxidation by comparative example, it is difficult to whole oxidation is fully achieved, also only rest on material surface modifying, to the internal Ni existed of positive pole material granule structure profound level simultaneously2+But the efficient oxidation cannot be realized.
Embodiment 2
(1) by 3.0355gMnCl2·2H2O、1.6432gNiSO4·6H2O and .2145gCo(NO3)2·6H2O is dissolved in respectively in deionized water and makes 1mol L-1Solution, 7gNaOH and 5.7062g(NH4)2S2O8It is dissolved in respectively in deionized water and is configured to 2mol L-1Solution；
(2) being mixed in 250mL flask by manganese chloride, nickel sulfate, cobalt nitrate solution, 50 DEG C of oil bath heating, 900rpm stirs, and adds 22.5mL ammonia, obtains complex compound sediment；
(3) 50 DEG C, sodium hydroxide solution and ammonium persulfate solution are added drop-wise to complex compound sediment respectively under 900rpm mechanical agitation, and control the pH value of system between 11.00 ~ 11.50 with ammonia, keep 50 DEG C, the continuously stirred 12h of 900rpm, under 50 DEG C of environment, stand 2h, obtain intermediate precipitation；
(4) gained intermediate precipitation being filtered, wash 2 times, at 120 DEG C of vacuum drying 8h, gained intermediate product weight 1.8894g, then with 1.4520gLi2CO3Mix homogeneously, puts into batch-type furnace, is warming up to 700 DEG C with the programming rate of 3 DEG C/min in air atmosphere, and constant temperature keeps 6h, natural cooling, obtains the nickeliferous lithium-rich manganese-based anode material of 2.4001g.
Embodiment 3
(1) by 5gMn(NO3)2·4H2O、3gNiCl2·6H2O and 0.2gMgCl2·6H2O is dissolved in respectively in deionized water and makes 0.5mol L-1Solution, 10gKOH and 8g potassium dichromate is dissolved in respectively in deionized water and is configured to 1mol L-1Solution；
(2) being mixed in 250mL flask by manganese nitrate, Nickel dichloride., magnesium chloride solution, 600rpm stirs, and adds 30g oxalic acid and tartaric acid, obtains complex compound sediment；
(3) 20 DEG C, potassium hydroxide solution and potassium bichromate solution are added drop-wise to complex compound sediment respectively under 600rpm mechanical agitation, and control the pH value of system between 11.50 ~ 12.00 with ammonia, keep 20 DEG C, the continuously stirred 15h of 600rpm, under 20 DEG C of environment, stand 3h, obtain intermediate precipitation；
(4) gained intermediate precipitation is filtered, wash 2 times, natural drying, gained intermediate product weight 3g, then mix homogeneously with 6g Lithium hydrate, be placed in oxygen-containing atmosphere 300 DEG C calcining 24h and obtain nickeliferous lithium-rich manganese-based anode material.
Embodiment 4
(1) by 3gMnSO4, 1.5gNi(NO3)2And 0.1gCd(NO3)2·4H2O is dissolved in respectively in methanol and makes 2mol L-1Solution, 5g sodium carbonate and 4g potassium permanganate are dissolved in respectively in methanol and are configured to 5mol L-1Solution；
(2) being mixed in 250mL flask by manganese sulfate, nickel nitrate, chromium nitrate solution, 90 DEG C of oil bath heating, 50rpm stirs, and adds 10gEDTA, obtains complex compound sediment；
(3) 90 DEG C, sodium carbonate liquor and potassium permanganate solution are added drop-wise to complex compound sediment respectively under 50rpm mechanical agitation, and control the pH value of system between 10.00 ~ 10.50 with ammonia, keep 90 DEG C, the continuously stirred 10h of 50rpm, under 90 DEG C of environment, stand 1h, obtain intermediate precipitation；
(4) gained intermediate precipitation is filtered, wash 2 times, spray drying, gained intermediate product weight 1.2g, then mix homogeneously with 0.6g lithium acetate, be placed in oxygen-containing atmosphere 1000 DEG C calcining 3h, obtain nickeliferous lithium-rich manganese-based anode material.
Embodiment 5
(1) by 10gMnCl2·4H2O、20gNiSO4·7H2O and 1gZrO2It is dissolved in respectively in ethanol and makes 1mol L-1Solution, 10g potassium bicarbonate and 6g sodium peroxydisulfate are dissolved in respectively in ethanol and are configured to 2mol L-1Solution；
(2) being mixed in 500mL flask by manganese chloride, nickel sulfate, zirconia solution, 60 DEG C of oil bath heating, 500rpm stirs, and adds 25g orthophenanthroline, obtains complex compound sediment；
(3) 60 DEG C, potassium bicarbonate solution and sodium peroxydisulfate solution are added drop-wise to complex compound sediment respectively under 500rpm mechanical agitation, and control the pH value of system between 10.50 ~ 11.50 with ammonia, keep 60 DEG C, the continuously stirred 12h of 500rpm, under 60 DEG C of environment, stand 2h, obtain intermediate precipitation；
(4) gained intermediate precipitation is filtered, wash 2 times, 80 DEG C of vacuum drying 24h, gained intermediate product weight 4g, then mix homogeneously with 4g lithium fluoride, be placed in air atmosphere 1000 DEG C calcining 5h, obtain nickeliferous lithium-rich manganese-based anode material.
Embodiment 6
(1) by 5gMnCl2、5gNiSO4And 0.3gTiO2It is dissolved in methanol/ethanol mixed solution respectively and makes 1mol L-1Solution, 4g sodium hydroxide and 2g potassium peroxydisulfate are dissolved in methanol/ethanol mixed solution respectively and are configured to 2mol L-1Solution；
(2) being mixed in 250mL flask by manganese chloride, nickel sulfate, titanium oxide solution, 50 DEG C of oil bath heating, 600rpm stirs, and adds 5g mercaptoethylmaine, obtains complex compound sediment；
(3) 50 DEG C, sodium hydroxide solution and potassium persulfate solution are added drop-wise to complex compound sediment respectively under 600rpm mechanical agitation, and control the pH value of system between 10.50 ~ 11.00 with ammonia, keep 50 DEG C, the continuously stirred 15h of 600rpm, under 50 DEG C of environment, stand 1h, obtain intermediate precipitation；
(4) gained intermediate precipitation is filtered, wash 2 times, 120 DEG C of vacuum drying 5h, gained intermediate product weight 1.5g, then mix homogeneously with 2g lithium carbonate, be placed in air atmosphere 400 DEG C calcining 16h, obtain nickeliferous lithium-rich manganese-based anode material.
Embodiment 7
The positive pole of lithium ion battery generally includes plus plate current-collecting body and positive electrode, and collector is known to ordinary skill in the art, for collecting the electric current resulting from positive pole and providing effective electric interface, electric current is caused external circuit.The material of collector can select from the material generally selected based on the present invention, such as aluminium foil.
Lithium ion battery also includes negative pole, barrier film and electrolyte.
The negative pole of battery includes negative current collector and negative electrode active material.Negative current collector can be the material generally selected, such as Copper Foil；Negative electrode active material can be the material generally selected, such as graphite.
Barrier film is arranged between positive pole and negative pole, it is possible to is the non-conducting of a kind of solid or Ins. ulative material, positive pole and negative pole is separated, and make both mutually insulateds, thus preventing short circuit, and barrier film can allow for ion and transmits between a positive electrode and a negative electrode, generally adopts polypropylene and/or polyethylene.
Electrolyte at least includes electrolyte and organic solvent.Electrolyte can include but are not limited to lithium hexafluoro phosphate, LiBF4, lithium perchlorate.One skilled in the art will appreciate that lithium salts can effectively increase electrolytical ionic conductivity.Electrolytical organic solvent can be common organic aqueous solution, such as ether, vinyl carbonate, propylene carbonate, diethyl carbonate etc..
By the nickeliferous lithium-rich manganese-based anode material of the nickel-rich positive pole material of comparative example and embodiment 1 respectively by positive electrode: superconduction electrical carbon (SP): the mass ratio of poly-inclined tetrafluoroethene (PVDF)=8:1:1 is coated on aluminium foil, lithium metal is adopted to do electrode, celgard barrier film, 2032 button cells it are fabricated in high-purity argon gas glove box, carrying out charge and discharge cycles test, cycle performance curve is as shown in Figure 6.It can be seen that embodiment 1(curve 1) positive electrode circulate 115 weeks after, capacity remains the 90.69% of initial capacity, and the positive electrode of comparative example (curve 2) capacity after circulation 115 weeks only keeps 75.15%.This is that internal due to embodiment 1 positive electrode granule and surface nickel element is all substantially oxidized, thus improving uniformity and the stability of positive electrode, and then improves cyclical stability and the high rate performance of battery.
The above; being only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any those skilled in the art of belonging to are in the technical scope that the invention discloses; the change that can readily occur in or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with scope of the claims.
Claims (10)
1. the preparation method of a nickeliferous lithium-rich manganese-based anode material, it is characterised in that comprise the following steps:
S1, nickel source, manganese source, doped chemical source, chelating agent, strong oxidizer, precipitant solvent are configured to solution；
S2, by nickel source, manganese source and doped chemical source solution mix, under stirring condition add chelating agent, obtain complex compound sediment；
Under S3, stirring condition, strong oxidant solution and precipitant solution are added complex compound sediment, and with the pH value of ammonia control system, until precipitation completely, obtains intermediate precipitation；
S4, intermediate precipitation is filtered, washing and dry, then mix with lithium source, after calcining, obtains nickeliferous lithium-rich manganese-based anode material.
2. preparation method according to claim 1, it is characterised in that the formula of described nickeliferous lithium-rich manganese-based anode material is LixNiyMnzMwO2, wherein: 1≤x≤4/3,0≤y≤1,2/3≤z≤1, w=1-y-z, doped chemical M is at least one in Co, Al, Cr, Fe, Ti, V, Mg, Zn, Cu, Mo, Zr.
3. preparation method according to claim 1, it is characterised in that described nickel source is NiSO4、NiSO4·6H2O、NiSO4·7H2O, Ni(NO3)2, Ni(NO3)2·6H2O、NiCl2And NiCl2·6H2At least one in O；Described manganese source is MnSO4、MnSO4·4H2O, Mn(NO3)2·4H2O、MnCl2、MnCl2·2H2O、MnCl2·4H2O、MnCl3、K2MnO4And KMnO4In at least one；Described doped chemical source is at least one in the sulfate of doped chemical M, nitrate, chloride, oxide；Doped chemical M is at least one in Co, Al, Cr, Fe, Ti, V, Mg, Zn, Cu, Mo, Zr.
4. preparation method according to claim 1, it is characterized in that, described chelating agent is at least one in ammonia, oxalic acid, citric acid, tartaric acid, sulfosalicylic acid, orthophenanthroline, dimercaptopropanol, BAL, Unithiol, mercaptoethylmaine, TGA, thiourea, oxine, triethanolamine, EDTA, EGTA, ethylenediamine tetrapropionic acid and triethylenetetramine.
5. preparation method according to claim 1, it is characterised in that described strong oxidizer is at least one in peroxide, bichromate, permanganate；Described precipitant is at least one in sodium hydroxide, potassium hydroxide, carbonate and bicarbonate.
6. preparation method according to claim 1, it is characterised in that described solvent is at least one in water, methanol, ethanol, propanol and ether.
7. preparation method according to claim 1, it is characterised in that described lithium source is at least one in lithium carbonate, Lithium hydrate, lithium acetate and lithium fluoride.
8. a nickeliferous lithium-rich manganese-based anode material, it is characterised in that described nickeliferous lithium-rich manganese-based anode material preparation method according to any one of claim 1 ~ 7 is prepared from.
9. the positive pole of a battery, it is characterised in that described positive pole includes the nickeliferous lithium-rich manganese-based anode material described in claim 8.
10. a battery, including positive pole, negative pole, barrier film and electrolyte, it is characterised in that described positive pole includes the nickeliferous lithium-rich manganese-based anode material described in claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610123666.5A CN105742595A (en) | 2016-03-04 | 2016-03-04 | Nickel-containing lithium-rich and manganese-based positive electrode material and preparation method thereof, positive electrode and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610123666.5A CN105742595A (en) | 2016-03-04 | 2016-03-04 | Nickel-containing lithium-rich and manganese-based positive electrode material and preparation method thereof, positive electrode and battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105742595A true CN105742595A (en) | 2016-07-06 |
Family
ID=56249955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610123666.5A Pending CN105742595A (en) | 2016-03-04 | 2016-03-04 | Nickel-containing lithium-rich and manganese-based positive electrode material and preparation method thereof, positive electrode and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105742595A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532037A (en) * | 2017-01-13 | 2017-03-22 | 哈尔滨工业大学 | Preparation method of vanadium-molybdenum-doped lithium ion battery cathode material |
| CN109904548A (en) * | 2019-03-22 | 2019-06-18 | 郑州中科新兴产业技术研究院 | A method of synthesizing rich lithium material from waste and old lithium ion battery |
| CN110459758A (en) * | 2019-08-16 | 2019-11-15 | 安徽工业大学 | A method of preparing lithium-ion-power cell high pressure lithium-rich manganese-based anode material |
| CN111403727A (en) * | 2019-11-11 | 2020-07-10 | 余姚市鑫和电池材料有限公司 | Preparation method of modified ternary cathode material with high capacity and long service life |
| CN112038613A (en) * | 2020-09-17 | 2020-12-04 | 贵州大学 | Modification method for realizing doped coating of high-nickel ternary cathode material by preprocessing precursor |
| CN112079398A (en) * | 2020-09-03 | 2020-12-15 | 浙江中金格派锂电产业股份有限公司 | Preparation method and application of gradient composite doped lithium-rich manganese-based material |
| CN112242515A (en) * | 2020-09-28 | 2021-01-19 | 乳源东阳光磁性材料有限公司 | Preparation method and application of modified lithium-rich manganese-based layered oxide positive electrode material |
| CN114408983A (en) * | 2021-12-24 | 2022-04-29 | 合肥国轩电池材料有限公司 | Lithium transition metal oxide and preparation method and application thereof |
| CN114695885A (en) * | 2020-12-30 | 2022-07-01 | 山东海科创新研究院有限公司 | Positive electrode of high-nickel lithium ion battery and lithium ion battery |
| CN115340129A (en) * | 2022-09-01 | 2022-11-15 | 中国科学院合肥物质科学研究院 | Spinel phase epitaxial coated lithium-manganese sulfide-rich material and preparation method and application thereof |
| CN116588993A (en) * | 2023-07-17 | 2023-08-15 | 宜宾光原锂电材料有限公司 | Ternary precursor, preparation method thereof, lithium battery positive electrode material and lithium battery |
| CN117164022A (en) * | 2023-11-03 | 2023-12-05 | 河南科隆新能源股份有限公司 | Modified cobalt-free lithium-rich manganese-based precursor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881889A (en) * | 2012-10-15 | 2013-01-16 | 福建师范大学 | Method for preparing lithium-enriched solid solution cathode material by two-section direct temperature-rise sintering method |
| CN105118983A (en) * | 2015-09-16 | 2015-12-02 | 湖北宇电能源科技股份有限公司 | Method for preparing lithium nickel manganese oxide anode material |
-
2016
- 2016-03-04 CN CN201610123666.5A patent/CN105742595A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881889A (en) * | 2012-10-15 | 2013-01-16 | 福建师范大学 | Method for preparing lithium-enriched solid solution cathode material by two-section direct temperature-rise sintering method |
| CN105118983A (en) * | 2015-09-16 | 2015-12-02 | 湖北宇电能源科技股份有限公司 | Method for preparing lithium nickel manganese oxide anode material |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532037A (en) * | 2017-01-13 | 2017-03-22 | 哈尔滨工业大学 | Preparation method of vanadium-molybdenum-doped lithium ion battery cathode material |
| CN109904548A (en) * | 2019-03-22 | 2019-06-18 | 郑州中科新兴产业技术研究院 | A method of synthesizing rich lithium material from waste and old lithium ion battery |
| CN110459758A (en) * | 2019-08-16 | 2019-11-15 | 安徽工业大学 | A method of preparing lithium-ion-power cell high pressure lithium-rich manganese-based anode material |
| CN110459758B (en) * | 2019-08-16 | 2022-03-25 | 安徽工业大学 | Method for preparing high-voltage lithium-rich manganese-based positive electrode material of lithium ion power battery |
| CN111403727B (en) * | 2019-11-11 | 2022-10-14 | 余姚市鑫和电池材料有限公司 | Preparation method of modified ternary cathode material |
| CN111403727A (en) * | 2019-11-11 | 2020-07-10 | 余姚市鑫和电池材料有限公司 | Preparation method of modified ternary cathode material with high capacity and long service life |
| CN112079398A (en) * | 2020-09-03 | 2020-12-15 | 浙江中金格派锂电产业股份有限公司 | Preparation method and application of gradient composite doped lithium-rich manganese-based material |
| CN112038613A (en) * | 2020-09-17 | 2020-12-04 | 贵州大学 | Modification method for realizing doped coating of high-nickel ternary cathode material by preprocessing precursor |
| CN112242515A (en) * | 2020-09-28 | 2021-01-19 | 乳源东阳光磁性材料有限公司 | Preparation method and application of modified lithium-rich manganese-based layered oxide positive electrode material |
| CN114695885A (en) * | 2020-12-30 | 2022-07-01 | 山东海科创新研究院有限公司 | Positive electrode of high-nickel lithium ion battery and lithium ion battery |
| CN114408983A (en) * | 2021-12-24 | 2022-04-29 | 合肥国轩电池材料有限公司 | Lithium transition metal oxide and preparation method and application thereof |
| CN115340129A (en) * | 2022-09-01 | 2022-11-15 | 中国科学院合肥物质科学研究院 | Spinel phase epitaxial coated lithium-manganese sulfide-rich material and preparation method and application thereof |
| CN116588993A (en) * | 2023-07-17 | 2023-08-15 | 宜宾光原锂电材料有限公司 | Ternary precursor, preparation method thereof, lithium battery positive electrode material and lithium battery |
| CN116588993B (en) * | 2023-07-17 | 2023-09-26 | 宜宾光原锂电材料有限公司 | Ternary precursor, preparation method thereof, lithium battery positive electrode material and lithium battery |
| CN117164022A (en) * | 2023-11-03 | 2023-12-05 | 河南科隆新能源股份有限公司 | Modified cobalt-free lithium-rich manganese-based precursor and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742595A (en) | Nickel-containing lithium-rich and manganese-based positive electrode material and preparation method thereof, positive electrode and battery | |
| CN107275633B (en) | Gradient fluorine-doped ternary cathode material with low lattice stress and preparation method thereof | |
| CN106784686A (en) | A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof | |
| CN105514373A (en) | Positive electrode material of high-capacity lithium ion battery and preparation method of positive electrode material | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN105692721A (en) | Sodium ion battery positive electrode material, and preparation method and application method thereof | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN114162881B (en) | Preparation method of anion in-situ doped high-nickel ternary cathode material | |
| CN111063881A (en) | Preparation method of NCM ternary positive electrode material modified by adjusting lithium source oxidation | |
| CN104733714B (en) | Modification method of lithium ion battery cathode material | |
| CN106602024A (en) | In-situ surface-modified lithium-rich material and preparation method thereof | |
| CN108091832A (en) | Nickel cobalt transition metal oxide anode material for lithium ion battery and preparation method | |
| CN104051709A (en) | Preparation method of lithium ion battery positive electrode material | |
| CN103715422B (en) | Electrolysis prepares the method for the nickelic system positive electrode of lithium ion battery | |
| CN113060773A (en) | Preparation method and application of full-concentration-gradient high-nickel ternary material | |
| CN111682174B (en) | Antimony-coated lithium battery positive electrode material and preparation method and application thereof | |
| CN115763766A (en) | Na 2 MnPO 4 F-coated O3 type layered sodium-ion battery positive electrode material and preparation method thereof | |
| CN115966687A (en) | Layered sodium-ion battery positive electrode material and preparation method and application thereof | |
| CN110112387B (en) | Titanium suboxide coated and modified cathode material and preparation method thereof | |
| CN116639740A (en) | Cobalt-free lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN114933292B (en) | Preparation method and application of lithium iron phosphate | |
| CN112002878A (en) | Preparation method of ternary gradient material with manganese-rich surface layer | |
| CN103236532B (en) | Preparation method for lithium ion battery positive electrode material with 4.5 V voltage platform | |
| CN115911331A (en) | Preparation method of low-nickel copper manganese-based sodium ion battery positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20190705 |