CN109428060A - A kind of preparation method and application of cladded type multilayer presoma - Google Patents

A kind of preparation method and application of cladded type multilayer presoma Download PDF

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CN109428060A
CN109428060A CN201710748778.4A CN201710748778A CN109428060A CN 109428060 A CN109428060 A CN 109428060A CN 201710748778 A CN201710748778 A CN 201710748778A CN 109428060 A CN109428060 A CN 109428060A
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presoma
core
cladded type
shell
clad
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刘孟
毕玉敬
王德宇
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • 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
    • H01M4/36—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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

This application discloses a kind of preparation method of cladded type multilayer precursor, the method is at least included the following steps: obtaining core presoma；Shell presoma is coated into core presoma by dry mixed, wet ball grinding or the method for co-precipitation.The present processes have many advantages, such as it is easy to operate, it is applied widely.

Description

A kind of preparation method and application of cladded type multilayer presoma
Technical field
This application involves a kind of preparation method and applications of cladded type multilayer presoma, belong to field of material preparation.
Background technique
Lithium ion battery is a kind of migrated between inside battery positive and negative anodes using lithium ion to realize energy stores and release The chemical energy storage device put.Due to lithium ion battery have energy density is high, operating voltage is high, have extended cycle life with it is environmental-friendly The advantages that, it is widely used in electronics and communications industry, and be gradually applied to the power electrics such as electric car and hybrid vehicle Pond field.Therefore, the security performance of lithium ion battery and high rate performance also have attracted more and more attention from people.Studies have shown that lithium Ion battery electrode reaction occurs in electrode/electrolyte interface, so improving the effective ways of positive electrode chemical property is Surface covering cladding is carried out to material.
Currently, most of method for coating are handled for material after sintering, need to exist sintered active material It is handled in aqueous solution, this method for coating, covering amount is less, cannot form uniform clad, and clad substance does not have electrification Activity is learned, cannot have lithium ion deintercalation ability, lithium ion can be hindered in the transmission of surface/interface, battery polarization is caused to increase, Reduce the high rate performance and energy density of material.It would therefore be highly desirable to provide a kind of preparation method of cladded type material.
Summary of the invention
According to the one aspect of the application, a kind of preparation method of cladded type multilayer presoma is provided, this method is passed through Thick and uniform clad can be obtained, is used for the core-shell material of preparation for field of lithium ion battery；As lithium ion Cell positive material, clad have electro-chemical activity and lithium ion transport ability, can obstruct electrode material and electrolyte It directly contacts, reduces the side reaction of inside battery, improve security performance, simultaneously as the clad has lithium ion transport energy Power limited can slow down the impedance increase during circulating battery.
The structure of the cladded type multilayer presoma are as follows: inside is core presoma, and clad is the forerunner of shell substance Body.
The preparation method of the cladded type multilayer presoma at least includes the following steps:
(1) core presoma is obtained；
(2) shell presoma is coated into core presoma by dry mixed, wet ball grinding or the method for co-precipitation；
Wherein, it when the number of plies of clad >=2, is then successively coated according to the direction far from core, each clad substance Between cannot form solid solution.
Preferably, the preparation method of the core presoma includes at least following steps: by each member in core presoma The salting liquid mixing of element, stirs, filters, washing, it is dry to get.
Preferably, the partial size of the core presoma is 1-25 μm, preferably 1-20 μm.
Preferably, the core presoma is NiyCoz(Mn, Al)uM1-y-z-u(OH)2、NiyCoz(Mn, Al)uM1-y-z-uO2、 Co1-wNw(OH)2、Co1-wNwO2、Co1-wNwOOH、Mn1-j/2Qj/2(OH)2、Mn1-j/2Qj/2OOH、Mn1-j/2Qj/2O2、Fe1-sRsPO4In One kind；
Wherein, M is selected from least one of Cr, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, Sn, Zn；
N in Cr, Al, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, V, La, Mn, Pb, Sn, Y, La, Zn at least It is a kind of；
Q is selected from least one of Co, Cr, Al, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, V, Zn；
R is selected from least one of Mn, Ni, Mg, Co, Cu, Zn, Ti, Li, Na, K, Ag, Al；
0≤y≤1,0≤< z≤0.5,0≤u≤0.5；
0≤w≤0.5,0≤j≤0.5,0≤s≤1.0.
Preferably, the preparation method of the core presoma includes at least following steps:
(i) under inert gas atmosphere, the solution of tri- kinds of salt of Ni, Co, Mn is added in ammonia spirit, while ammonia is added Water and lye (the preferably aqueous solution of alkali, such as the aqueous solution of NaOH) adjusting solution ph are 7-14, after sedimentation, continue to stir 1-20 hours, core presoma Ni will be obtained after precipitating filtering, washing, dryingyCoz(Mn, Al)uM1-y-z-u(OH)2, or will obtain NiyCoz(Mn, Al)uM1-y-z-u(OH)2Low-temperature sintering obtains core presoma NiyCoz(Mn, Al)uM1-y-z-uO2。
Or,
Reaction kettle is added simultaneously in iron salt solutions and phosphorus source solution, while it is 1- that ammonium hydroxide and lye adjusting solution ph, which is added, 8, after sedimentation, continue stirring 1-20 hours, core presoma Fe will be obtained after precipitating filtering, washing, drying1-sRsPO4。
Wherein, Ni, Co, Mn salt are respectively selected from the solubilities such as sulfate, nitrate, chloride, the acetate of Ni, Co, Mn At least one of salt.
The molysite is selected from least one of ferric sulfate, ferric nitrate, iron chloride, acetate.
Phosphorus source be selected from phosphoric acid, ammonium dihydrogen phosphate, triammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, At least one of diammonium hydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate.
The alkali is at least one of NaOH, LiOH, KOH.
Preferably, the preparation method of the core presoma includes at least following steps:
(i) under inert gas atmosphere, the solution of two kinds of salt of N, Co is added in ammonia spirit, at the same be added ammonium hydroxide and Lye (the preferably aqueous solution of alkali, such as the aqueous solution of NaOH) adjusting solution ph is 7-14, after sedimentation, continues to stir 1-20 Hour, core presoma Co will be obtained after precipitating filtering, washing, drying1-wNw(OH)2；
Or the Co that will be obtained1-wNw(OH)2Low-temperature sintering obtains core presoma Co1-wNwO2；
Or in Co1-wNw(OH)2Hydrogen peroxide is added in solution, continues to stir, core will be obtained after precipitating filtering, washing, drying Core presoma Co1-wNw OOH。
Preferably, the preparation method of the core presoma includes at least following steps:
(i) under inert gas atmosphere, the solution of two kinds of salt of Mn, Q is added in ammonia spirit, at the same be added ammonium hydroxide and Lye (the preferably aqueous solution of alkali, such as the aqueous solution of NaOH) adjusting solution ph is 7-14, after sedimentation, continues to stir 1-20 Hour, core presoma Mn will be obtained after precipitating filtering, washing, drying1-j/2Qj/2(OH)2；
Or the Mn that will be obtained1-j/2Qj/2(OH)2Low-temperature sintering obtains core presoma Mn1-j/2Qj/2O2；
Or in Mn1-j/2Qj/2(OH)2Hydrogen peroxide is added in solution, continues to stir, will be obtained after precipitating filtering, washing, drying Core presoma Mn1-j/2Qj/2OOH。
Preferably, the method that core presoma is coated described in step (2) at least includes the following steps:
(a1) salting liquid of the element containing shell is mixed, regulation system pH value with material to be covered, is stirred, washed, it is dry, Obtain cladded type presoma；
(b1) it repeats the above steps n-1 times, n is the positive integer more than or equal to 1, obtains cladded type multilayer presoma；
Wherein, material to be covered is core presoma or cladded type presoma；
Step (a1) is different with the shell element in (b1).
Preferably, the salting liquid of the element containing shell is in the sulfate of shell element, nitrate, chloride, acetate At least one.
Preferably, the molar ratio of the salting liquid of the element containing shell and material to be covered is 0.01~0.03 in step (a1): 1。
Preferably, the method that core presoma is coated described in step (2) at least includes the following steps:
(a2) by least one of the nano-scale oxide of the element containing shell, hydroxide, oxyhydroxide with wait wrap Material mixing is covered to get cladded type presoma；
(b2) it repeats the above steps n-1 times, n is the positive integer more than or equal to 1, obtains cladded type multilayer presoma；
Wherein, material to be covered is core presoma or cladded type presoma；
Step (a2) is different with the shell element in (b2).
Preferably, step (a1), cladded type presoma described in step (a2) clad independently selected from the oxidation of A At least one of object, hydroxide, oxyhydroxide；
Wherein, A is in Nb, Zr, Ta, Y, Sb, Mo, La, Pb, Bi, In, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti, Zn At least one.
In step (b1), step (b2) clad of cladded type presoma independently selected from the oxide of B, hydroxide, At least one of oxyhydroxide, phosphate；
Wherein, B is selected from least one of Co, Fe, Ni, Mn.
Preferably a kind of method for coating core presoma, at least includes the following steps:
(ii) solution of A salt is added in the reaction kettle for being provided with core presoma, pH value is adjusted using lye, makes A Hydroxide sedimentation or be adsorbed on core presoma surface.Wherein, A salt be Nb, Zr, Ta, Y, Sb, Mo, La, Pb, Bi, In, W, any one in the soluble-salt (such as sulfate, nitrate, chloride, acetate) of Sn, Ga, Cd, Sc, Ba, V, Cr, Ti, Zn The molar ratio of kind or two or more combinations, A salt and presoma P are between 0.01-0.30, in lye NaOH, LiOH, KOH Any one or two or more combinations.According to the different controls of selection salt type in different numerical value, adjustable range is final pH 1-14。
(iii) substance that (ii) is obtained is mixed with B salting liquid, or is mixed in B salting liquid and lye, adjusting pH value is 2- 14, so that the hydroxide of B is continued to settle or is adsorbed on the hydroxide of A.The mixed solution with lye and ammonium hydroxide can be passed through It adjusts pH value of solution and comes control settlement rate and crystal morphology.Reacted solution is continued into stirring 5-24 hours, after filtering, drying The multilayer presoma of cladded type is obtained, drying temperature is 50-200 DEG C.Wherein, B salt is sulfate, the nitre of Co, Fe, Ni, Mn, Ti The molar ratio of any one in the soluble-salts such as hydrochlorate, chloride, acetate or two or more combinations, B salt and presoma P exist Between 0.01-0.30, any one in lye NaOH, LiOH, KOH or two or more combinations.
Preferably, step (ii), the pH value of system is adjusted to 10.5-12 in (iii).
The preparation method of cladded type multilayer presoma described herein is applied to prepare core-shell material.
The another aspect of the application provides a kind of preparation method of core-shell material, and it is more to include at least above-mentioned cladded type The preparation of layer presoma.
Preferably, the method also includes following steps:
The cladded type multilayer presoma being prepared is sintered；
Or, the cladded type multilayer presoma for preparing to obtain is mixed with the raw material containing Li, it is sintered；
Preferably, the molar ratio of the raw material containing Li and cladded type multilayer presoma is 0.98-1.20:1；Wherein, contain The molal quantity of the raw material of Li is in terms of the molal quantity of Li element in raw material, and the molal quantity of cladded type multilayer presoma is in presoma The molal quantity meter of metallic element.
Wherein, the raw material containing Li is selected from least one of lithium carbonate, lithium hydroxide, lithium chloride, lithium nitrate, lithium acetate.
It is further preferred that the method also includes following steps:
(iv) the multilayer presoma of cladded type is uniformly mixed with lithium salts, uniformly mixed material is burnt in oxygenous atmosphere Knot, obtains positive electrode.
Wherein, the multilayer presoma molar ratio 0.98-1.20:1 of lithium salts and cladded type, lithium salts be lithium carbonate, lithium hydroxide, One or more of lithium chloride, lithium nitrate, lithium acetate.
Sintering atmosphere is one or more of air, oxygen, nitrogen/oxygen, argon gas/oxygen；Preferably, sintering temperature It is divided into two sections, first segment sintering temperature is 400-700 DEG C, and constant temperature time is 2-24 hours, and second segment sintering temperature is 700- 1000 DEG C, sintering time is 10-36 hours, pulverizes and sieves, obtains product.
The thickness of shell is in 1-500nm in the core-shell material that the method is prepared.
The thickness of shell is in 1-100nm in the core-shell material that the method is prepared.
Preferably, the thickness of shell is in 100-500nm in the core-shell material that the method is prepared.
Preferably, the partial size of the core-shell material is 1-30 μm, preferably 1-25 μm.
Preferably, the method also includes following steps:
Obtained product will be sintered to mix with the salting liquid containing C, adjust pH, by dry mixed, wet ball grinding or be total to Precipitating is reacted, and is calcined, and the core-shell material for the oxide that outermost layer is C is obtained；
Preferably, C is selected from Al, Mg, Zr, Zn, Y, Ta, Cr, Nb, Mo, V, Ti, Ga, Sr, Ba, W, Sb, Sn, Cd, Bi, Pb At least one of.
It is further preferred that the method also includes following steps:
(v) material for obtaining step (iv) sintering into the water, forms dispersion liquid, the solution of celite is added, together after stirring When be added lye, adjusting pH value is 5-14, and material surface after sintering coats the hydroxide of one layer of C, obtains surface cladding There is the positive electrode of the hydroxide of C.It is calcined after filtering, obtains to surface and be coated with the positive electrode of the oxide of C.
Wherein, celite Al, Mg, Zr, Zn, Y, Ta, Cr, Nb, Mo, V, Ti, Ga, Sr, Ba, W, Sb, Sn, Ga, Cd, Bi, Pb Soluble-salt in any one or two or more combinations, one or more of lye NaOH, LiOH, KOH.
Final ph is according to the different controls of selection salt type in different numerical value.Calcination temperature is 300-700 DEG C, calcines gas Atmosphere is air or oxygen.
(i), (ii), (iii), the preparation method that (iv) is a kind of preferably core-shell material.
(i), (ii), (iii), (iv), the preparation method that (v) is a kind of preferably core-shell material, i.e. core-shell material Outermost layer be protective oxide film, allow the material to steady operation under high voltages.
Preferably, the shell of the core-shell material has the function of electro-chemical activity and lithium ion transport.
The above-mentioned pH adjusting being related to is all made of lye and/or ammonium hydroxide is adjusted, wherein it is 1.0 that lye, which is selected from concentration, At least one of the alkali metal hydroxide of~3.0mol/L, alkaline earth metal hydroxide；The concentration of ammonium hydroxide be 1.0~ 1.5mol/L。
The another aspect of the application provides a kind of anode material for lithium-ion batteries, the anode material for lithium-ion batteries The core-shell material being prepared containing the method.
The application's in another aspect, provides a kind of lithium ion battery, includes the anode material for lithium-ion batteries.
The lithium ion cell positive, can be used for using organic solvent or aqueous solution as in the lithium ion battery of electrolyte just Pole material, it may also be used for using the positive electrode in the lithium ion battery of solid electrolyte.
The preparation method of the lithium ion battery: positive electrode and conductive agent acetylene black and binder Kynoar are existed It is uniformly mixed in N-methyl pyrrolidones (NMP) solvent, the mass ratio of positive electrode, conductive agent and binder is 85:10:5, will Uniformly mixed slurry is coated on aluminium foil, dry, and lithium ion cell positive is made.
The beneficial effect that the application can generate includes:
1) preparation method provided herein, have many advantages, such as it is easy to operate, it is applied widely.
2) shell of preparation method provided herein, the core-shell material being prepared is uniform, overcomes the prior art Middle to be first sintered shell covering amount present in the method coated again few, coats non-uniform defect.
3) preparation method provided herein, when being used to prepare anode material for lithium-ion batteries, so that lithium ion anode Material has uniform clad, and clad has electro-chemical activity and lithium ion transport ability, improves the electrical property of material Energy.
Detailed description of the invention
Fig. 1 is the shape appearance figure of presoma P1 in embodiment 1；
Fig. 2 is the shape appearance figure of presoma P4 in embodiment 4；
Fig. 3 is the shape appearance figure of product C4 in embodiment 4；
The SEM figure that Fig. 4 is product C4 in embodiment 4；
The cycle performance figure that Fig. 5 is C4 in C1 and embodiment 4 in embodiment 1；
The cycle performance figure that Fig. 6 is C5 in C2 and embodiment 5 in embodiment 2；
The cycle performance figure that Fig. 7 is C6 in C3 and embodiment 6 in embodiment 3；
The high rate performance figure that Fig. 8 is C4 in C1 and embodiment 4 in embodiment 1；
The high rate performance figure that Fig. 9 is C5 in C2 and embodiment 5 in embodiment 2；
The high rate performance figure that Figure 10 is C6 in C3 and embodiment 6 in embodiment 3.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources.
Analysis method is as follows in embodiments herein:
It is analyzed using the scanning electron microscope S4800H pattern test of Japanese Hitachi production.
Chemical property is carried out using the LAND electrochemical test system CT2001A of Wuhan Xin Nuo Electronics Co., Ltd. production Test analysis.
Embodiment 1 prepares tertiary cathode material C1
Molar ratio according to Ni, Co, Mn is that 8:1:1 prepares mixed solution, weighs six water nickel nitrates, six water nitric acid respectively The dissolution of 100mL water is added in cobalt, four water manganese nitrate 46.53g, 5.82g, 5.02g.Prepare 1000mL 2mol/L NaOH and The mixed solution of 1.5mol/L ammonium hydroxide.
In the reaction kettle of argon gas protection, 200mL water is added, by the NaOH solution and 2mol/L of mixed solution and 2mol/L Ammonia spirit simultaneously be added in reaction kettle, solution final pH control after 11.5, sedimentation, filtration washing will be precipitated, Presoma P1, chemical composition Ni are obtained after 80 DEG C of drying0.8Co0.1Mn0.1(HO)2。
Above-mentioned P1 presoma 10g is weighed, is mixed according to lithium salts with presoma molar ratio 1.05:1, LiOHH is weighed2O 4.77g is uniformly mixed with presoma, is sintered 12 hours at 850 DEG C, is obtained product, can be used for positive electrode, and C1 is labeled as.
Embodiment 2 prepares lithium iron phosphate positive material C2
Nine water ferric nitrate 40.40g, diammonium hydrogen phosphate 13.21g are weighed, 100mL deionized water dissolving is separately added into, obtains Iron nitrate solution and diammonium hydrogen phosphate solution.Prepare the ammonia spirit of 100mL 2mol/L.
Under protection of argon gas, iron nitrate solution and ammonium dibasic phosphate solution are added in reaction kettle simultaneously, it is molten with ammonium hydroxide Liquid adjusts pH value 5 or so.It is stirred 4 hours at 40 DEG C, after sedimentation, filtration washing will be precipitated, before obtaining after 80 DEG C of drying Drive body P2, chemical composition FePO4。
Above-mentioned P2 presoma 10g is weighed, is mixed according to lithium salts with presoma molar ratio 1.08:1, LiOHH is weighed2O 3.00g is uniformly mixed with presoma, after 450 DEG C are sintered 6 hours, is sintered 10 hours at 750 DEG C, obtained product can be used for Positive electrode is labeled as C2.
Embodiment 3 prepares lithium cobaltate cathode material C3
Weigh Co3O450g is 1.05 according to lithium salts and presoma molar ratio, weighs LiOHH2O27.44g and Co3O4It is mixed Close uniformly, under oxygen atmosphere 600 DEG C sintering 6 hours after, 900 DEG C be sintered 10 hours, obtain lithium cobaltate cathode material, mark For C3.
Embodiment 4 prepares core-shell material C4
Presoma P1 10g is weighed, 100mL water is added, is stirred, dispersion liquid is formed.Prepare 1mol/L ammonia spirit.It weighs 2.265g Zr(SO4)2·4H2O adds 60mL water to dissolve.
By Zr (SO4)2Solution is added in the dispersion liquid of presoma P1, after addition, adjusts pH to 8.0, mistake with ammonium hydroxide Filter, washing three times, obtain surface cladding ZrO (OH) after 100 DEG C of dryings2Presoma P3.
10g presoma P3 is weighed, 100mL water is added, stirring forms dispersion liquid, weighs 2.92g Co (CH3COO)2·4H2O is molten Solution is in 12mL water.Prepare LiOH the and 1.5mol/L ammonium hydroxide mixed solution of 30mL 2mol/L.
By Co (CH3COO)2LiOH the and 1.5mol/L ammonium hydroxide mixed solution of solution and 2mol/L are added to presoma simultaneously In the dispersion liquid of P3, by Co (OH)2It is deposited in the surface presoma P3, sedimentation pH control is 12, and filtering is washed, after 100 DEG C of dryings Obtain composite precursor P4.
It weighs above-mentioned P4 presoma 10g, lithium salts and presoma P4 to mix according to the ratio of molar ratio 1.2:1, weigh LiOH·H2O 5.33g is uniformly mixed with presoma P4, after 480 DEG C are sintered 6 hours, are sintered 12 hours, are obtained at 950 DEG C Core is LiNi0.8Co0.1Mn0.1O2, shell is amorphous phase Li6Zr2O7With crystal phase LiCoO2Core-shell material, be labeled as C4.
Embodiment 5 prepares core-shell material C5
10g presoma P2 is weighed, 100mL water is added, stirring forms dispersion liquid.Prepare 30mL 1mol/L ammonia spirit.It weighs 7.04g tantalic chloride adds 14mL water to dissolve.
Tantalic chloride solution is added in the dispersion liquid of presoma P2, after addition, with ammonium hydroxide adjust pH to 8.0~ 9.0 filtering, washing three times, obtains surface cladding Ta (OH) after 100 DEG C of dryings5Presoma P5.
Presoma P5 20g is weighed, 200mL water is added, stirring forms dispersion liquid.Molar ratio according to Ni, Co, Mn is 5:2:3 Mixed solution is prepared, weighs nickel sulfate hexahydrate 1.62g, cobalt sulfate 0.39g, manganese sulfate monohydrate 0.63g respectively, 12mL is added Water dissolution.
LiOH the and 1.5mol/L ammonia spirit of Ni, Co, Mn mixed solution and 2mol/L are added to presoma simultaneously In dispersion liquid, by Ni0.5Co0.3Mn0.2(OH)2It is deposited in the surface presoma P5, sedimentation pH control is 11.5.Filtering washing, 100 Composite precursor P6 is obtained after DEG C dry.
It weighs above-mentioned P6 presoma 10g, lithium salts and presoma to mix according to the ratio of molar ratio 1.1, weighs LiOHH2O 2.98g is uniformly mixed with presoma P6, after 500 DEG C are sintered 6 hours, is sintered 12 hours at 850 DEG C, obtaining core is LiFePO4, shell is amorphous phase LiTaO3With crystal phase LiNi0.5Co0.3Mn0.2O2Core-shell material, be labeled as C5.
Embodiment 6 prepares core-shell material C6
Weigh 50g Co3O4With 8.79g Y2O3, obtain presoma P7 within 350r/min ball milling 6 hours；Weigh presoma 10g P7 and 1.15g MnO2, obtain presoma P8 within 400r/min ball milling 6 hours；
Wherein, Co3O4And Y2O3For nanoscale, specification is purity >=99.9%, 50~60nm of partial size.
Lithium salts is mixed with presoma P8 according to molar ratio 1.05:1, weighs above-mentioned P8 presoma 10g and LiOHH2O 5.23g, 400r/min ball milling 6 hours, under oxygen atmosphere 600 DEG C sintering 6 hours after, 900 DEG C be sintered 10 hours, obtain core Core is LiCoO2, shell is amorphous phase LiYO2With crystal phase LiMn2O4Core-shell material, be labeled as C6.
Embodiment 7 prepares lithium ion battery
Product C1~C6 will be prepared in Examples 1 to 6 as positive electrode and conductive agent acetylene black and binder to gather Vinylidene (PVDF) is uniformly mixed in N-methyl pyrrolidones (NMP) solvent；Wherein, positive electrode, conductive agent and bonding The mass ratio of agent is 85:10:5, and uniformly mixed slurry is coated on aluminium foil, is dried in vacuo 12 hours at 120 DEG C, and lithium is made Ion battery anode, respectively D1~D6.
It the use of above-mentioned D1~D6 is anode, using lithium metal as cathode, electrolyte uses the carbonic acid of 1mol/L lithium hexafluoro phosphate The solution of vinyl acetate and dimethyl carbonate, diaphragm use 20 microns thick of polyethylene and PP composite material, are assembled into CR2032 type button lithium ion battery, is respectively labeled as DC1~DC6.The button cell being assembled into carries out charge-discharge test, voltage Range is 2.8-4.3 volts.
The morphology characterization of 8 material of embodiment
Electronic Speculum morphology analysis, typical pattern such as FIG. 1 to FIG. 3 institute are scanned to presoma P1~P8,1~C6 of material C Show, the appearance of other materials with it is as shown in the figure similar.Wherein, presoma P1 in Fig. 1 corresponding embodiment 1；Fig. 2 corresponding embodiment 4 Middle presoma P4；Product C4 in Fig. 3 corresponding embodiment 4.It can be seen from the figure that the partial size of the presoma of core-shell material be 1~ 25 μm, core-shell material is the spheric granules that partial size is 1~26 μm；The sectional view of the SEM of product C4 in Fig. 4 corresponding embodiment 4, from As can be seen that product C4 is core-shell structure, crystal phase LiCoO in shell in figure2It is evenly distributed on amorphous phase Li6Zr2O7In.
The electric property of 9 material of embodiment characterizes
By 1~C6 of material C carry out cycle performance test, condition are as follows: discharge voltage be 4.3~2.8V, discharge-rate 1C, Typical case is as shown in Fig. 5~Fig. 7.Wherein, in Fig. 5 corresponding embodiment 1 C1 and the C4 in embodiment 4 cycle performance figure, Fig. 6 is corresponding In embodiment 2 in C2 and embodiment 5 C5 cycle performance figure, in Fig. 7 corresponding embodiment 3 in C3 and embodiment 6 C6 cyclicity It can figure.Can significantly it find out from figure, there is the core-shell material with core structure and shell more excellent capacity to keep Rate, cycle performance are more excellent.
High rate performance test is carried out to 1~C6 of material C, typical performance is as shown in Fig. 8~Figure 10.Wherein, Fig. 8 is corresponding real Apply the high rate performance figure of the C1 and C4 in embodiment 4 in example 1, in Fig. 9 corresponding embodiment 2 in C2 and embodiment 5 C5 it is forthright again Can figure, in Figure 10 corresponding embodiment 3 in C3 and embodiment 6 C6 high rate performance figure.It can be seen from the figure that having core structure There is more excellent specific discharge capacity with the core-shell material of shell, high rate performance is more excellent.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to Case study on implementation is imitated, is belonged in technical proposal scope.

Claims (10)

1. a kind of preparation method of cladded type multilayer presoma, which is characterized in that at least include the following steps:
(1) core presoma is obtained；
(2) shell presoma is coated into core presoma by dry mixed, wet ball grinding or the method for co-precipitation；
Wherein, it when the number of plies of clad >=2, is then successively coated according to the direction far from core；And each clad substance it Between cannot form solid solution.
2. the method according to claim 1, wherein the core presoma is NiyCoz(Mn, Al)uM1-y-z-u (OH)2、NiyCoz(Mn, Al)uM1-y-z-uO2、Co1-wNw(OH)2、Co1-wNwO2、Co1-wNwOOH、Mn1-j/2Qj/2(OH)2、Mn1-j/ 2Qj/2OOH、Mn1-j/2Qj/2O2、Fe1-sRsPO4One of；
Wherein, M is selected from least one of Cr, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, Sn, Zn；
N in Cr, Al, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, V, La, Mn, Pb, Sn, Y, La, Zn at least one Kind；
Q is selected from least one of Co, Cr, Al, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, V, Zn；
R is selected from least one of Mn, Ni, Mg, Co, Cu, Zn, Ti, Li, Na, K, Ag, Al；
0≤y≤1,0≤< z≤0.5,0≤u≤0.5；
0≤w≤0.5,0≤j≤0.5,0≤s≤1.0.
3. the method according to claim 1, wherein coating the method for core presoma extremely described in step (2) Less the following steps are included:
(a1) salting liquid of the element containing shell is mixed, regulation system pH value with material to be covered, is stirred, washed, it is dry, it obtains Cladded type presoma；
(b1) it repeats the above steps n-1 times, n is the positive integer more than or equal to 1, obtains cladded type multilayer presoma；
Wherein, material to be covered is core presoma or cladded type presoma；
Step (a1) is different with the shell element in (b1)；
Preferably, the salting liquid of the element containing shell is in the sulfate of shell element, nitrate, chloride, acetate At least one.
4. according to the method described in claim 3, it is characterized in that, the salting liquid of the element containing shell described in step (a1) with to The molar ratio of covering material is 0.01~0.03:1；
Preferably, the clad of cladded type presoma described in step (a1) is independently selected from the oxide of A, hydroxide, hydroxyl At least one of base oxide；
Wherein, A in Nb, Zr, Ta, Y, Sb, Mo, La, Pb, Bi, In, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti, Zn extremely Few one kind；
The clad of cladded type presoma is independently selected from the oxide of B, hydroxide, oxyhydroxide, phosphorus in step (b1) At least one of hydrochlorate；
Wherein, B is selected from least one of Co, Fe, Ni, Mn.
5. the method according to claim 1, wherein coating the method for core presoma extremely described in step (2) Less the following steps are included:
(a2) by least one of the nano-scale oxide of the element containing shell, hydroxide, oxyhydroxide, phosphate with to Covering material mixes to get cladded type presoma；
(b2) it repeats the above steps n-1 times, n is the positive integer more than or equal to 1, obtains cladded type multilayer presoma；
Wherein, material to be covered is core presoma or cladded type presoma；
Step (a2) is different with the shell element in (b2)；
Preferably, the clad of cladded type presoma described in step (a2) is independently selected from the oxide of A, hydroxide, hydroxyl At least one of base oxide；
Wherein, A in Nb, Zr, Ta, Y, Sb, Mo, La, Pb, Bi, In, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti, Zn extremely Few one kind；
The clad of cladded type presoma is independently selected from the oxide of B, hydroxide, oxyhydroxide, phosphorus in step (b2) At least one of hydrochlorate；
Wherein, B is selected from least one of Co, Fe, Ni, Mn.
6. a kind of preparation method of core-shell material, which is characterized in that the method includes at least any one of claim 1 to 5 institute The preparation for the clad presoma stated.
7. according to the method described in claim 6, it is characterized in that, the method also includes following steps:
The cladded type multilayer presoma being prepared is mixed with the raw material containing Li, is sintered；Wherein, raw material and packet containing Li The molar ratio for covering type multilayer presoma is 0.98~1.20:1；
Wherein, the molar ratio of the raw material containing Li is calculated with the molal quantity of Li；The molar ratio of cladded type multilayer presoma is with cladded type The molal quantity of metallic element in multilayer precursor calculates；
Preferably, carbonate of the raw material containing Li selected from Li, hydroxide, chloride, nitrate, in acetate at least It is a kind of.
8. the method according to the description of claim 7 is characterized in that the method also includes following steps:
The product that sintering obtains is mixed with the salting liquid containing C, pH is adjusted, passes through dry mixed, wet ball grinding or co-precipitation It is reacted, is calcined, obtain the core-shell material for the oxide that outermost layer is C；
Wherein, C in Al, Mg, Zr, Zn, Y, Ta, Cr, Nb, Mo, V, Ti, Ga, Sr, Ba, W, Sb, Sn, Cd, Bi, Pb extremely Few one kind.
9. a kind of anode material for lithium-ion batteries, which is characterized in that the anode material for lithium-ion batteries is wanted containing with good grounds right The core-shell material for asking any one of 6 to 8 the methods to be prepared.
10. a kind of lithium ion battery, which is characterized in that include anode material for lithium-ion batteries as claimed in claim 9.
CN201710748778.4A 2017-08-28 2017-08-28 A kind of preparation method and application of cladded type multilayer presoma Pending CN109428060A (en)

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