CN106450194B - A kind of manganese base shape richness lithium material and its preparation method with uniform lithium phosphate clad - Google Patents
A kind of manganese base shape richness lithium material and its preparation method with uniform lithium phosphate clad Download PDFInfo
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- CN106450194B CN106450194B CN201610895892.5A CN201610895892A CN106450194B CN 106450194 B CN106450194 B CN 106450194B CN 201610895892 A CN201610895892 A CN 201610895892A CN 106450194 B CN106450194 B CN 106450194B
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- 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
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- 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
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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
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- 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
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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 technical field of lithium ion, disclose a kind of manganese base shape richness lithium material and its preparation method with uniform lithium phosphate clad.The preparation method the following steps are included: secure ph range be 8~9 trishydroxymethylaminomethane hydrochloric acid salt buffer solution, then manganese base shape richness lithium material is added under agitation, after stirring 1~2h, adds dopamine hydrochloride, 24~48h is stirred, precursor C is obtained；Lithium phosphate is added in precursor C under agitation, is heated while stirring, until only solid is remaining, obtains predecessor D；Predecessor D is placed in 700~800 DEG C of Muffle furnaces burning 10~for 24 hours to get to the manganese base shape richness lithium material with uniform lithium phosphate clad.The high capacity with uniform lithium phosphate clad and high rate capability manganese base shape richness lithium material that preparation method of the present invention obtains have high specific capacity, high high rate performance and good cycle performance.
Description
Technical field
The invention belongs to technical field of lithium ion, in particular to a kind of manganese base with uniform lithium phosphate clad
Shape richness lithium material and its preparation method.
Background technique
In recent years, due to manganese base layered oxide (Li [LixMnyNz]O2, N=metallic element, x+y+z=1) have compared with
(> 3.5V vs Li/Li under high operating potential+) its theoretical discharge specific capacity is up to 200mAh g-1Be widely noticed above and
Research.Its high specific energy is expected to become the anode material for lithium-ion batteries of next-generation high-energy density.
But at present apparently, the bottleneck of manganese base layered oxide development is lower electronics and ionic conductivity and cyclicity
Energy.Low conductivity by internal non-electroactive Li2MnO3What composition was influenced, and cycle performance is then due to being circulated throughout
The irreversible structure transformation of inside caused by journey and the dissolution of serious transition metal ions and electrolyte material under high voltages
Caused by the catalysis oxidation for expecting surface.The former can coat electronic conduction object or nanosizing processing by surface to improve its conductance
Rate, and the latter is other than the irreversible transformation for the internal structure that can not be resisted, point of transition metal ions dissolution and electrolyte
Solution then can coat inertia protective layer by surface to be alleviated.Coating layer material mainly has metal oxide, fluorination at present
Object and phosphate etc..However, most of electronics and ionic conductivity are all very low in these coatings, although manganese can be improved
The cyclical stability of base richness lithium, but the performance of its high rate performance can be further decreased.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of with uniform
The preparation method of the manganese base shape richness lithium material of lithium phosphate clad.
Another object of the present invention is that the manganese base shape with uniform lithium phosphate clad for providing above method preparation is rich
Lithium material.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of the manganese base shape richness lithium material with uniform lithium phosphate clad, specifically includes following step
It is rapid:
(1) the hydrochloric acid salt buffer solution for the trishydroxymethylaminomethane that secure ph range is 8~9, then in stirring speed
Degree is 800~1000rmin-1Under conditions of manganese base shape richness lithium material is added, after stirring 1~2h, then with 1000~
1500r·min-1Mixing speed be added dopamine hydrochloride, stir 24~48h, obtain precursor C；
(2) low whipping speed is 900~1300rmin-1Under conditions of by lithium phosphate be added to step (1) it is obtained before
It drives in object C, heats while stirring, until only solid is remaining, obtain predecessor D；
(3) predecessor D made from step (2) is placed in 700~800 DEG C of Muffle furnaces burning 10~for 24 hours to get to having
The manganese base shape richness lithium material of uniform lithium phosphate clad.
The process for preparation of the hydrochloric acid salt buffer solution of trishydroxymethylaminomethane is as follows in step (1): low whipping speed is
300~600rmin-1Under conditions of trishydroxymethylaminomethane is dissolved into deionized water, stir 0.5~2h, obtain molten
Liquid A；Then low whipping speed is 500~800rmin-1Under conditions of by hydrochloric acid solution with it is per second 0.25~2 drop speed be added dropwise
Into solution A, with the pH value of pH meter real-time detection solution A, when making range 8~9 of pH value, stops dropwise addition hydrochloric acid solution and obtain
Solution B, i.e. the hydrochloric acid salt buffer solution of trishydroxymethylaminomethane；Wherein, the concentration of trishydroxymethylaminomethane is in solution A
0.01~1molL-1；The concentration of hydrochloric acid solution is 0.1~12molL-1。
The hydrochloric acid for the trishydroxymethylaminomethane that the amount that manganese base shape richness lithium material is added described in step (1) is every 1L
The corresponding manganese base shape richness lithium material that 1~100g is added of salt buffer solution, the addition dopamine hydrochloride refer to every 1L's
The corresponding dopamine hydrochloride that 1~10mmol is added of the hydrochloric acid salt buffer solution of trishydroxymethylaminomethane.
Lithium phosphate described in step (2) can be at least one of anhydrous phosphoric acid lithium and hypophosphite monohydrate lithium；
The molar ratio of manganese base shape richness lithium material used in lithium phosphate used in step (2) and step (1) is 1:45
~270.
The molecular formula of manganese base shape richness lithium material described in step (1) is Li [LixMnyNz]O2(x+y+z=1),
In, at least one of N Co, Ni, Fe, Ru, Ti, Al etc..
Above-mentioned manganese base shape richness lithium material is prepared by following methods:
(I) the molecular formula Li [Li of manganese base shape richness lithium material is pressedxMnyNz]O2It is corresponding to choose corresponding manganese salt, element N
Salt, under conditions of then low whipping speed is 300~1000r/min in deionized water by manganese salt, the corresponding salt dissolution of element N
Form solution；The manganese salt can be at least one of manganese acetate, manganese chloride, manganese nitrate and manganese sulfate；N pairs of the element
The salt answered can be at least one of acetate, chlorate, nitrate and the sulfate of element N；The element N be it is a kind of or
More than one metallic element；Wherein the concentration of manganese salt is 0.2~2mol L-1, the total concentration of the corresponding salt of element N is 0.005
~2mol L-1；
(II) by oxalic acid aqueous isopropanol with 0.5~2 drop/s under conditions of low whipping speed is 300~1000r/min
Speed is added drop-wise in the solution in step (I), then is centrifugated product with the revolving speed of 10000~20000r/min, with anhydrous second
Alcohol washs 3~5 times, and 60~150 DEG C dry 12~for 24 hours, obtain oxalate precursor；Wherein, oxalic acid aqueous isopropanol
Concentration is 0.5~2mol/L, and the volume ratio of solution and oxalic acid aqueous isopropanol obtained in step (I) is 1:(0.4~2.5).
(III) oxalate precursor for obtaining step (II) and lithium carbonate and potassium chloride 1:(0.5~0.6 in molar ratio):
After (5~10) are sufficiently mixed, 750~850 DEG C are heated to the heating rate of 2~5 DEG C/min in the atmosphere of air or oxygen
Processing 10~for 24 hours, is cooled to room temperature and is washed with deionized 3~5 times again, finally it is dried in vacuo 12 in 100~150 DEG C~for 24 hours
Up to manganese base shape richness lithium material.
A kind of high capacity and high rate capability manganese base prepared by the above method with uniform lithium phosphate clad
Stratiform richness lithium material.
Mechanism of the invention are as follows:
It is uniformly sunk using the strong adsorption capacity that the autohemagglutination ability and autohemagglutination of dopamine form poly-dopamine as lithium phosphate
Important bridge of the product in manganese base shape richness lithium material.Dopamine is a kind of biological reagent, is widely present in nature biotechnology.It
Autohemagglutination can occur, autohemagglutination mild condition is easily-controllable.The polymer of autohemagglutination and life --- poly-dopamine has extremely strong adsorption capacity,
It can be adsorbed on almost any shape of any material surface easily, and thickness is uniform.Therefore, by dopamine in manganese base
The polymerization of shape richness lithium material Adsorption on Surface becomes one layer of uniform thickness poly-dopamine, then deposits lithium phosphate on the surface thereof, due to
The uniformity of poly-dopamine is adsorbed, so that the lithium phosphate deposited equally has uniform thickness.Finally again at high temperature will in
Interbed poly-dopamine oxidizes away, and leaves the manganese base shape richness lithium material of internal layer and the lithium phosphate of outer layer, therefore obtain final
Product is the manganese base shape richness lithium material with uniform lithium phosphate clad.Lithium phosphate have extremely stable electrochemicaUy inert and
Low molecular weight is good lithium ion conductor, at low cost, does not need secondary operation, and the stable circulation of manganese base richness lithium can be improved
Property.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) the manganese base shape richness lithium material with uniform lithium phosphate clad that preparation method of the present invention obtains has high
Specific capacity, high high rate performance and good cycle performance.
(2) simply, in reaction free from admixture generates preparation method of the present invention, and reaction process is efficient and convenient, does not need to introduce multiple
Miscellaneous operating process.
(3) present invention enables later lithium phosphate to be uniformly deposited on its surface, reaches using dopamine as cladding medium
To equally distributed effect.It is acted on again by high-temperature oxydation and removes poly-dopamine layer, obtain the lithium phosphate packet of only uniform thickness
The manganese base shape richness lithium material covered.Can material surface be all completely wrapped in this way, obstruct electrolyte and material
On the one hand the direct contact on surface can reduce transition metal of the electrolyte under high potential with the high catalytic action of material surface
It reacts and is oxidized decomposition；On the other hand it then plays a protective role, caused by can effectively slowing down material in cyclic process
Transition metal dissolution.Thus improve the cyclical stability of material.Simultaneously as lithium phosphate is good lithium ion conductor,
Therefore reduce polarity effect of the material under high current density, thus improve the high rate performance of material.
Detailed description of the invention
Fig. 1 is manganese base shape richness lithium material with uniform lithium phosphate clad prepared by embodiment 1 and the preparation of comparative example 1
Manganese base shape richness oxidate for lithium SEM figure；
Fig. 2 is manganese base shape richness lithium material with uniform lithium phosphate clad prepared by embodiment 2 and the preparation of comparative example 2
Manganese base shape richness oxidate for lithium TEM figure；
Fig. 3 is manganese base shape richness lithium material with uniform lithium phosphate clad prepared by embodiment 3 and the preparation of comparative example 3
Manganese base shape richness oxidate for lithium production lithium ion battery charge-discharge magnification performance comparison figure；
Fig. 4 is manganese base shape richness lithium material with uniform lithium phosphate clad prepared by embodiment 4 and the preparation of comparative example 4
Manganese base shape richness oxidate for lithium production lithium ion battery charge-discharge performance comparison diagram.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
If agents useful for same can routinely be bought without specified otherwise from market in embodiment.
Embodiment 1
A kind of preparation side of high capacity and high rate capability manganese base shape richness lithium material with uniform lithium phosphate clad
Method, comprising the following steps:
(1) 100mL deionized water is added in the high neck beaker of 250mL, then low whipping speed is 300rmin-1's
Under the conditions of 1.5g trishydroxymethylaminomethane is added, and dissolve it sufficiently, obtain solution A；
(2) in 600rmin-1Mechanical stirring under, slowly with the speed of 3 drop per second in the solution A that is obtained to step (1)
1molL is added-1Hydrochloric acid solution and with the pH value of pH meter real-time detection solution A, so that its pH value is reached 8.0 stoppings and salt be added dropwise
Acid obtains solution B；
(3) 20mL deionized water is added in the high neck beaker of 100mL, then low whipping speed is 300rmin-1Item
5g manganese acetate and 1.7g nickel acetate are added under part, and keeps its fully dispersed, obtains mixed solution；
(4) in 1000rmin-1Mechanical stirring under, slowly with 1 drop per second in the mixed solution that is obtained to step (3)
20mL 1.36molL is added in speed-1Oxalic acid aqueous isopropanol, then at 20000rmin-1Under be centrifuged, with anhydrous second
Alcohol washs 5 times, and in 60 DEG C of vacuum drying 12h, obtains oxalate precursor；
(5) oxalate precursor and Li for obtaining step (4)2CO3It is in molar ratio that 1:0.525:5 is carried out sufficiently with KCl
Mixing；Mixture is sent into Muffle furnace, with 3 DEG C of min-1Rate be warming up to 800 DEG C, constant temperature 10h；It is cooled to room temperature and spends again
Ion water washing 5 times, finally in 120 DEG C of vacuum drying 12h, obtain manganese base shape richness lithium material Li [Li0.2Mn0.6Ni0.2]O2。
(6) in 1000rmin-1Mechanical stirring under, 1.2g is added in the solution B that obtains to step (2) by step (5)
Manganese base shape richness lithium material Li [Li obtained0.2Mn0.6Ni0.2]O2, stirring 1h is then proceeded to, then with 1200rmin-1Stirring
0.03g dopamine hydrochloride is added under speed, is further continued for stirring 28h, obtains precursor C；The wherein dopamine hydrochloride
Concentration be 1.5mmolL-1；The concentration of manganese base shape richness lithium material used is 11.5gL-1；
(7) in 900rmin-1Mechanical stirring under, 0.025g bis- is added in the precursor C that obtains to step (6) and is hydrated
Lithium phosphate is subsequently placed in 80 DEG C of heating stirrings to only solid and is left, obtains predecessor D；
(8) predecessor D made from step (7) is placed in 730 DEG C of Muffle furnace the 10h that burns, obtains that there is uniform phosphorus
The manganese base shape richness lithium material of sour lithium clad.
Embodiment 2
A kind of preparation side of high capacity and high rate capability manganese base shape richness lithium material with uniform lithium phosphate clad
Method, comprising the following steps:
(1) 200mL deionized water is added in the high neck beaker of 500mL, then low whipping speed is 600rmin-1's
Under the conditions of 2g trishydroxymethylaminomethane is added, and dissolve it sufficiently, obtain solution A；
(2) in 700rmin-1Mechanical stirring under, slowly with the speed of 1 drop per second in the solution A that is obtained to step (1)
2molL is added-1Hydrochloric acid solution and with the pH value of pH meter real-time detection solution A, so that its pH value is reached 8.5 stoppings and salt be added dropwise
Acid obtains solution B；
(3) 30mL deionized water is added in the high neck beaker of 100mL, then low whipping speed is 800rmin-1Item
10g manganese acetate, 5.1g nickel acetate and 5.1g cobalt acetate are added under part, and keeps its fully dispersed, obtains mixed solution；
(4) in 500rmin-1Mechanical stirring under, slowly with 0.5 drop per second in the mixed solution that is obtained to step (3)
Speed be added 50mL 1.63molL-1Oxalic acid aqueous isopropanol, then at 18000rmin-1Under be centrifuged, with anhydrous
Ethanol washing 3 times, and in 80 DEG C of vacuum drying 18h, obtain oxalate precursor；
(5) oxalate precursor and Li for obtaining step (4)2CO3It is in molar ratio that 1:0.535:8 is carried out sufficiently with KCl
Mixing；Mixture is sent into Muffle furnace, with 5 DEG C of min-1Rate be warming up to 850 DEG C, constant temperature 12h；It is cooled to room temperature and spends again
Ion water washing 3 times, finally in 110 DEG C of vacuum drying 18h, obtain manganese base shape richness lithium material Li [Li0.2Mn0.4Ni0.2Co0.2]
O2。
(6) in 900rmin-1Mechanical stirring under, 2g is added in the solution B that obtains to step (2) and is made by step (5)
Manganese base shape richness lithium material Li [Li0.2Mn0.4Ni0.2Co0.2]O2, stirring 1.2h is then proceeded to, then with 1500rmin-1Stir
Addition 0.1g dopamine hydrochloride under speed is mixed, stirring is further continued for for 24 hours, obtains precursor C；The wherein dopamine hydrochloride
Concentration be 2.5mmolL-1；The concentration of manganese base shape richness lithium material used is 9.8gL-1；
(7) in 1100rmin-1Mechanical stirring under, 0.02g lithium phosphate is added in the precursor C that obtains to step (6),
It is remaining to only solid to be subsequently placed in 60 DEG C of heating stirrings, obtains predecessor D；
(8) predecessor D made from step (7) is placed in 780 DEG C of Muffle furnace the 15h that burns, obtains that there is uniform phosphorus
The manganese base shape richness lithium material of sour lithium clad.
Embodiment 3
A kind of preparation side of high capacity and high rate capability manganese base shape richness lithium material with uniform lithium phosphate clad
Method, comprising the following steps:
(1) 80mL deionized water is added in the high neck beaker of 400mL, then low whipping speed is 500rmin-1Item
1.2g trishydroxymethylaminomethane is added under part, and dissolves it sufficiently, obtains solution A；
(2) in 800rmin-1Mechanical stirring under, slowly with the speed of 0.5 drop per second in the solution A that is obtained to step (1)
5molL is added in degree-1Hydrochloric acid solution and with the pH value of pH meter real-time detection solution A, so that its pH value is reached 8.2 stoppings and salt be added dropwise
Acid obtains solution B；
(3) 50mL deionized water is added in the high neck beaker of 100mL, then low whipping speed is 500rmin-1Item
8g manganese acetate, 1.9g nickel acetate, 2.4g cobalt acetate and 0.8g ferric nitrate are added under part, and keeps its fully dispersed, obtains mixing molten
Liquid；
(4) in 700rmin-1Mechanical stirring under, slowly with 2 drop per second in the mixed solution that is obtained to step (3)
30mL 1.45molL is added in speed-1Oxalic acid aqueous isopropanol, then at 19000rmin-1Under be centrifuged, with anhydrous second
Alcohol washs 4 times, and in 100 DEG C of vacuum drying 15h, obtains oxalate precursor；
(5) oxalate precursor and Li for obtaining step (4)2CO3It is in molar ratio that 1:0.515:10 is filled with KCl
Divide mixing；Mixture is sent into Muffle furnace, with 4 DEG C of min-1Rate be warming up to 750 DEG C, constant temperature 15h；It is cooled to room temperature and uses again
Deionized water is washed 4 times, finally in 100 DEG C of vacuum drying 13h, obtains manganese base shape richness lithium material Li
[Li0.2Mn0.5Ni0.12Fe0.03Co0.15]O2。
(6) in 850rmin-1Mechanical stirring under, 1.5g is added in the solution B that obtains to step (2) and is made by step (5)
The manganese base shape richness lithium material Li [Li obtained0.2Mn0.5Ni0.12Fe0.03Co0.15]O2, stirring 2h is then proceeded to, then with 1300r
min-1Mixing speed under be added 0.05g dopamine hydrochloride, be further continued for stirring 35h, obtain precursor C；It is more described in wherein
The concentration of bar amine hydrochlorate is 3.3mmolL-1；The concentration of manganese base shape richness lithium material used is 18.8gL-1；
(7) in 1000rmin-1Mechanical stirring under, 0.008g bis- is added in the precursor C that obtains to step (6) and is hydrated
Lithium phosphate is subsequently placed in 70 DEG C of heating stirrings to only solid and is left, obtains predecessor D；
(8) predecessor D made from step (7) is placed in 750 DEG C of Muffle furnace the 18h that burns, obtains that there is uniform phosphorus
The manganese base shape richness lithium material of sour lithium clad.
Embodiment 4
A kind of preparation side of high capacity and high rate capability manganese base shape richness lithium material with uniform lithium phosphate clad
Method, comprising the following steps:
(1) 50mL deionized water is added in the high neck beaker of 200mL, then low whipping speed is 450rmin-1Item
1.0g trishydroxymethylaminomethane is added under part, and dissolves it sufficiently, obtains solution A；
(2) in 500rmin-1Mechanical stirring under, slowly with the speed of 2 drop per second in the solution A that is obtained to step (1)
1.5molL is added-1Hydrochloric acid solution and with the pH value of pH meter real-time detection solution A, so that its pH value is reached 9.0 stoppings and salt be added dropwise
Acid obtains solution B；
(3) 60mL deionized water is added in the high neck beaker of 100mL, then low whipping speed is 400rmin-1Item
6g manganese acetate, 1.2g nickel acetate, 0.9g cobalt acetate and 1g aluminum nitrate are added under part, and keeps its fully dispersed, obtains solution；
(4) in 900rmin-1Mechanical stirring under, slowly with the speed of 1.5 drop per second in the solution that is obtained to step (3)
40mL 0.82molL is added in degree-1Oxalic acid aqueous isopropanol, then at 15000rmin-1Under be centrifuged, use dehydrated alcohol
Washing 3 times, and in 130 DEG C of vacuum drying 18h, obtain oxalate precursor；
(5) oxalate precursor and Li for obtaining step (4)2CO3It is in molar ratio that 1:0.52:7 is carried out sufficiently with KCl
Mixing；Mixture is sent into Muffle furnace, with 2.5 DEG C of min-1Rate be warming up to 830 DEG C, constant temperature 16h；It is cooled to room temperature and uses again
Deionized water is washed 5 times, finally for 24 hours in 150 DEG C of vacuum drying, obtains manganese base shape richness lithium material Li
[Li0.2Mn0.55Al0.06Ni0.11Co0.08]O2。
(6) in 950rmin-1Mechanical stirring under, 0.8g is added in the solution B that obtains to step (2) and is made by step (5)
The manganese base shape richness lithium material Li [Li obtained0.2Mn0.55Al0.06Ni0.11Co0.08]O2, stirring 1.5h is then proceeded to, then with 1000r
min-1Mixing speed under be added 0.01g dopamine hydrochloride, be further continued for stirring 28h, obtain precursor C；It is more described in wherein
The concentration of bar amine hydrochlorate is 1mmolL-1；The concentration of manganese base shape richness lithium material used is 16gL-1；
(7) in 900rmin-1Mechanical stirring under, 0.02g lithium phosphate is added in the precursor C that obtains to step (6),
It is remaining to only solid to be subsequently placed in 75 DEG C of heating stirrings, obtains predecessor D；
(8) predecessor D made from step (7) is placed in 800 DEG C of Muffle furnace and is burnt for 24 hours, obtain that there is uniform phosphorus
The manganese base shape richness lithium material of sour lithium clad.
Comparative example 1
Directly adopt the manganese base shape richness lithium material Li [Li in embodiment 10.2Mn0.6Ni0.2]O2。
Comparative example 2
Directly adopt the manganese base shape richness lithium material Li [Li in embodiment 20.2Mn0.4Ni0.2Co0.2]O2。
Comparative example 3
Directly adopt the manganese base shape richness lithium material Li [Li in embodiment 30.2Mn0.5Ni0.12Fe0.03Co0.15]O2。
Comparative example 4
Directly adopt the manganese base shape richness lithium material Li [Li in embodiment 40.2Mn0.55Al0.06Ni0.11Co0.08]O2。
Test case
(1) half-cell assembles: high capacity with uniform lithium phosphate clad prepared by embodiment 3 and embodiment 4 with
Manganese base shape richness lithium material prepared by high rate capability manganese base shape richness lithium material and comparative example 3 and comparative example 4, respectively with
Super P and PVDF 8:1:1 in mass ratio carry out slurrying and are coated with, and 1 × 1 pole piece are then cut into, using metal lithium sheet as cathode
It is assembled into half-cell.
(2) charge-discharge test: high capacity with uniform lithium phosphate clad prepared by embodiment 3 and embodiment 4 and
The lithium of manganese base shape richness lithium material production prepared by high rate capability manganese base shape richness lithium material and comparative example 3 and comparative example 4 from
Sub- battery carries out carrying out charge and discharge under constant current under different multiplying.
Fig. 3 is the high capacity and high rate capability manganese base shape richness with uniform lithium phosphate clad prepared by embodiment 3
The high rate performance comparison diagram of manganese base shape richness lithium material prepared by lithium material and comparative example 3.As seen from Figure 3, embodiment 3 is resulting
High capacity and high rate capability manganese base shape richness lithium material with uniform lithium phosphate clad are in 0.2C, 0.5C, 1C, 2C and 5C
(1C=200mAg-1) in multiplying power charge-discharge cycle, the specific capacity of embodiment 3 is respectively 233.2mAhg-1、211.1mAh·g-1、180.8mAh·g-1、157.4mAh·g-1And 118mAhg-1, and the specific capacity of comparative example 3 only has 229.1mAh respectively
g-1、197.5mAh·g-1、161.4mAh·g-1、133.7mAh·g-1And 45.6mAhg-1, followed by 70 rate charge-discharges
After ring, the specific capacity of embodiment 3 still maintains 173.6mAhg-1, and comparative example 3 only has 142.3mAhg-1, show this
High capacity and high rate capability manganese base shape richness lithium material prepared by invention with uniform lithium phosphate clad is than tradition side
The manganese base shape richness lithium material of method preparation has higher high rate performance and cycle performance.
Fig. 4 is the high capacity and high rate capability manganese base shape richness with uniform lithium phosphate clad prepared by embodiment 4
The charge-discharge performance comparison diagram of the lithium ion battery of manganese base shape richness lithium material production prepared by lithium material and comparative example 4.
As shown in Figure 4, the resulting high capacity and high rate capability manganese base shape richness lithium material with uniform lithium phosphate clad of embodiment 4
Discharge capacity after material recycles 100 times under 0.2C multiplying power is 176.4mAhg-1, capacity retention ratio 78.0%, and comparative example
Discharge capacity after 4 resulting manganese base shape richness lithium materials equally recycle 100 times is 133.7mAhg-1, capacity retention ratio is
58.4%.Show the high capacity and high rate capability manganese base shape richness lithium prepared by the present invention with uniform lithium phosphate clad
Material has preferable cycle performance than manganese base shape richness lithium material prepared by conventional method.
From the detection data of Fig. 3, Fig. 4 it is found that the height with uniform lithium phosphate clad that preparation method of the present invention obtains
Capacity and high rate capability manganese base shape richness lithium material have charge/discharge capacity height, good rate capability, and stable cycle performance.
Fig. 1 is the high capacity and high rate capability manganese base shape richness with uniform lithium phosphate clad prepared by embodiment 1
The SEM figure of manganese base shape richness lithium material prepared by lithium material and comparative example 1, from figure 1 it appears that the apparent knot of two kinds of materials
It is almost the same to be configured looks, illustrates that cladding processing in surface can't cause big variation to material surface.
Fig. 2 is the high capacity and high rate capability manganese base shape richness with uniform lithium phosphate clad prepared by embodiment 2
The TEM figure of manganese base shape richness lithium material prepared by lithium material and comparative example 2.From figure 2 it can be seen that the material of embodiment 2
Grain surface has all coated the uniform clad of a layer thickness, and 2 surface of comparative example is then very smooth, illustrates that lithium phosphate was depositing
The surface of material can be equably covered on very much in journey.It can effectively stop electrolyte to contact with the direct of material in this way, subtract
The catalysis oxidation of few electrolyte on the surface of the material is decomposed, meanwhile, clad can effectively reduce transition metal ions in charge and discharge
Irreversible dissolution in cyclic process and caused by capacity attenuation.Can simultaneously be effectively improve the whole ionic conductance of material
Rate, the mechanical structure of robust material, reduce material in charge and discharge process internal stress effect and caused by collapse division, thus
Improve the cyclical stability and high rate performance of material.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (6)
1. a kind of preparation method of the manganese base shape richness lithium material with uniform lithium phosphate clad, it is characterised in that including following
Step:
(1) secure ph range be 8~9 trishydroxymethylaminomethane hydrochloric acid salt buffer solution, then low whipping speed be
800~1000rmin-1Under conditions of manganese base shape richness lithium material is added, after stirring 1~2h, then with 1000~1500r
min-1Mixing speed be added dopamine hydrochloride, stir 24~48h, obtain precursor C；
(2) low whipping speed is 900~1300rmin-1Under conditions of lithium phosphate is added to precursor C made from step (1)
In, it heats while stirring, until only solid is remaining, obtains predecessor D；
(3) predecessor D made from step (2) is placed in 700~800 DEG C of Muffle furnaces burning 10~for 24 hours to get uniform to having
The manganese base shape richness lithium material of lithium phosphate clad.
2. the preparation method of the manganese base shape richness lithium material according to claim 1 with uniform lithium phosphate clad,
It is characterized in that:
The molecular formula of manganese base shape richness lithium material described in step (1) is Li [LixMnyNz]O2, wherein x+y+z=1, N Co,
At least one of Ni, Fe, Ru, Ti, Al.
3. the preparation method of the manganese base shape richness lithium material according to claim 2 with uniform lithium phosphate clad,
It is characterized in that the manganese base shape richness lithium material is prepared by following methods:
(I) the molecular formula Li [Li of manganese base shape richness lithium material is pressedxMnyNz]O2Corresponding manganese salt, the corresponding salt of element N are chosen, so
Manganese salt, the corresponding salt dissolution of element N are formed in deionized water under conditions of low whipping speed is 300~1000r/min afterwards
Solution；The manganese salt is at least one of manganese acetate, manganese chloride, manganese nitrate and manganese sulfate；The corresponding salt of element N
For at least one of the acetate of element N, chlorate, nitrate and sulfate；The element N is any or a kind of
Above metallic element；Wherein the concentration of manganese salt is 0.2~2mol L-1, the total concentration of the corresponding salt of element N is 0.005~
2mol L-1；
(II) by oxalic acid aqueous isopropanol with 0.5~2 drop/s speed under conditions of low whipping speed is 300~1000r/min
It is added drop-wise in the solution in step (I), then product is centrifugated with the revolving speed of 10000~20000r/min, washed with dehydrated alcohol
Wash 3~5 times, and 60~150 DEG C dry 12~for 24 hours, obtain oxalate precursor；Wherein, the concentration of oxalic acid aqueous isopropanol
For 0.5~2mol/L, the volume ratio of solution obtained in step (I) and oxalic acid aqueous isopropanol is 1:(0.4~2.5)；
(III) oxalate precursor for obtaining step (II) and lithium carbonate and potassium chloride 1:(0.5~0.6 in molar ratio): (5~
10) after being sufficiently mixed, 750~850 DEG C of processing are heated to the heating rate of 2~5 DEG C/min in the atmosphere of air or oxygen
10~for 24 hours, and it is cooled to room temperature and is washed with deionized 3~5 times again, finally it is dried in vacuo 12 in 100~150 DEG C~for 24 hours to obtain the final product
Manganese base shape richness lithium material.
4. the preparation method of the manganese base shape richness lithium material according to claim 1 with uniform lithium phosphate clad,
It is characterized in that:
Lithium phosphate described in step (2) is at least one of anhydrous phosphoric acid lithium and hypophosphite monohydrate lithium.
5. the preparation method of the manganese base shape richness lithium material according to claim 1 with uniform lithium phosphate clad,
It is characterized in that:
The process for preparation of the hydrochloric acid salt buffer solution of trishydroxymethylaminomethane is as follows in step (1): low whipping speed be 300~
600r·min-1Under conditions of trishydroxymethylaminomethane is dissolved into deionized water, stir 0.5~2h, obtain solution A；So
Low whipping speed is 500~800rmin afterwards-1Under conditions of by hydrochloric acid solution with it is per second 0.25~2 drop speed be added drop-wise to solution A
In, with the pH value of pH meter real-time detection solution A, when making range 8~9 of pH value, stops dropwise addition hydrochloric acid solution and obtains solution B,
That is the hydrochloric acid salt buffer solution of trishydroxymethylaminomethane；Wherein, in solution A trishydroxymethylaminomethane concentration be 0.01~
1mol·L-1；The concentration of hydrochloric acid solution is 0.1~12molL-1。
6. the preparation method of the manganese base shape richness lithium material according to claim 1 with uniform lithium phosphate clad,
It is characterized in that:
The hydrochloride for the trishydroxymethylaminomethane that the amount that manganese base shape richness lithium material is added described in step (1) is every 1L is slow
The corresponding manganese base shape richness lithium material that 1~100g is added of solution is rushed, the addition dopamine hydrochloride refers to three hydroxyls of every 1L
The corresponding dopamine hydrochloride that 1~10mmol is added of the hydrochloric acid salt buffer solution of aminomethane；
The molar ratio of manganese base shape richness lithium material used in lithium phosphate used in step (2) and step (1) be 1:45~
270。
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| CN108666526A (en) * | 2018-08-06 | 2018-10-16 | 北京工业大学 | A kind of lithium ion cell positive and prepare the device of lithium ion cell positive, method |
| CN109244366B (en) * | 2018-11-27 | 2021-03-02 | 国联汽车动力电池研究院有限责任公司 | Surface composite modification method of lithium-rich material and lithium-rich material prepared by same |
| CN109659538B (en) * | 2018-12-19 | 2022-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of rich lithium manganese-based oxide material based on coating of dopamine and lithium phosphate, product and application thereof |
| CN114256457B (en) * | 2021-12-31 | 2023-12-05 | 国联汽车动力电池研究院有限责任公司 | Lithium-rich manganese-based positive electrode material with homogeneous composite coating layer and preparation method thereof |
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