CN107611422A - A kind of method and purposes of the non-equivalent substitution Mn doping vario-property nickel ion dopeds of P - Google Patents
A kind of method and purposes of the non-equivalent substitution Mn doping vario-property nickel ion dopeds of P Download PDFInfo
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- CN107611422A CN107611422A CN201710591258.7A CN201710591258A CN107611422A CN 107611422 A CN107611422 A CN 107611422A CN 201710591258 A CN201710591258 A CN 201710591258A CN 107611422 A CN107611422 A CN 107611422A
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Abstract
The present invention provides a kind of P methods of non-equivalent substitution Mn doping vario-property nickel ion dopeds, substitutes a small amount of Mn to realize to LiNi using the non-equivalent of nonmetalloid P0.5Mn1.5O4Doping vario-property, by being introduced into a small amount of room in 16d positions to adjust the content of oxygen defect in material, optimize orderly, unordered spinel structure ratio in material.In preparation process, citric acid is first dissolved in appropriate deionized water, lithium source, manganese source, nickel source and phosphorus source is then sequentially added and obtains mixed solution, heats and stirs to mixed solution and be evaporated, then through predecomposition and heat treatment, produces the nickel ion doped of the non-equivalent doping of P.The nickel ion doped for the non-equivalent doping vario-properties of P that the present invention is prepared, tap density is high, purity is high and without dephasign, has good high rate performance and cycle performance.By 1000 circulation volume conservation rates it is about 93% under 10C multiplying powers, 87% is still up to by 1600 circulation volume conservation rates.
Description
Technical field
The invention belongs to field of energy source materials, and in particular to a kind of preparation method and its usage of modified nickel ion doped.
Background technology
Manganese base spinel structure positive electrode is because of its aboundresources, discharge voltage height, advantages of environment protection, it is considered to be
Most one of anode material for lithium-ion batteries of attraction.Due to Mn3+Disproportionated reaction and Jahn-Teller effects, the material
Cycle performance is poor, and especially high temperature cyclic performance is poor, seriously limits its extensive use.In addition, its high rate performance also needs
Improved in further, to meet the needs of electric automobile high-power output.The positive electrode of spinel structure mainly includes mangaic acid
Lithium LiMn2O4And nickel ion doped LiNi0.5Mn1.5O4Deng.LiNi0.5Mn1.5O4Theoretical capacity is 147mAhg-1, voltage platform
In 4.7-4.75V.With LiMn2O4Compare, its voltage platform is higher by about 15%, and its energy density is up to 690Wh kg-1, it is higher than
LiCoO2、LiFePO4And LiCo1/3Ni1/3Mn1/3O2.The high-energy-density of Ni-based mangaic acid lithium-spinel structure makes it in electronic vapour
Car or other electrokinetic cell fields have broad application prospects.
Spinel structure LiNi0.5Mn1.5O4There are two kinds of space structures, Yi ZhongshiThe unordered spinelle knot of space group
Structure, another kind are the ordered structures of P4332 space groups.In disordered structure the diffusion path of lithium ion be by tetrahedron 8a positions to
Empty 16c positions, lithium ion is along two paths diffusions of 8c-4a and 8c-12d in ordered structure.Pass through coulomb potential calculation ratio
Relatively understand, when lithium ion spreads in three of the above path, 8c-4a is easiest to, and 8a-16c takes second place, and 8c-12d is most difficult to.Due to orderly
In structure, most easy diffusion path proportion only has 25%.Therefore, unordered spinel structure material is more beneficial for lithium ion expansion
Dissipate.Unordered spinel structure material generally there are a small amount of oxygen defect, due to oxygen defect presence its there is higher electrical conductivity,
And design feature makes lithium ion be more conducive to spread and transport.Therefore, its high rate performance is often compared with orderly spinel structure
It is more excellent.Orderly spinel structure can show more excellent cycle performance because it is generally not present Mn3+.Cause
This, can be by adulterating and controlling the content of oxygen defect in material, the ratio of orderly, unordered spinel structure in controlled material,
It can reach the purpose of optimization material combination property.
In the method for existing doping vario-property nickel ion doped, the element of doping is usually metallic element, is seldom adulterated nonmetallic
Element.In patent of the present invention, we are based on valence state and between oxygen have compared with strong bonding energy and adulterate by non-equivalent to introduce
Lattice vacancy improves electric conductivity and considered, the Mn for substituting 16d crystalline substances position using the non-equivalent of nonmetalloid P is realized to LiNi0.5Mn1.5O4
Doping vario-property, optimize material in orderly, unordered spinel structure ratio, realize the optimization of material combination property.
The content of the invention
For the above-mentioned problems in the prior art, an object of the present invention is to provide a kind of high rate performance and followed
The preparation method of the excellent nickel ion doped of ring performance, more particularly to a kind of non-equivalent substitution Mn doping vario-property nickel ion dopeds of P
Method.This method step is simple, efficiency high, cost are low and suitable large-scale production, what the P being prepared using this method was adulterated
Nickel ion doped lithium purity is high and without dephasign, using the P doping nickel ion dopeds of the present invention as positive pole be made the high rate performance of battery with
Cycle performance is excellent.
The modification nickel ion doped being prepared it is another object of the present invention to propose methods described.
Third object of the present invention is to propose the purposes of the modified nickel ion doped.
The technical scheme for realizing above-mentioned purpose of the present invention is：
A kind of method of the non-equivalent substitution Mn doping vario-property nickel ion dopeds of P, is substituted a small amount of using the non-equivalent of nonmetalloid P
Mn realize to LiNi0.5Mn1.5O4Doping vario-property, by being introduced into a small amount of room in 16d positions to adjust oxygen defect in material
Content, optimize material in orderly, unordered spinel structure ratio, realize the optimization of material combination property；In preparation process
In, citric acid is first dissolved in appropriate deionized water, lithium source, manganese source, nickel source and phosphorus source is then sequentially added and obtains mixed solution,
Heat and stir to mixed solution and be evaporated, then through predecomposition and heat treatment, produce the nickel ion doped that the non-equivalent of P is adulterated.
Described method, specifically includes step：
(1) citric acid is dissolved in deionized water, obtains clear solution；
(2) add lithium source, manganese source, nickel source and phosphorus source in the clear solution obtained to step (1), stirring, obtain mixing molten
Liquid；
(3) mixed solution that step (2) obtains is stirred, is evaporated to mixed solution, obtains xerogel；
(4) xerogel for obtaining step (3) carries out predecomposition, obtains predecomposition product；
(5) the predecomposition product for obtaining step (4) carries out the heat treatment of two-step sintering, obtains the nickel of the non-equivalent doping of P
LiMn2O4.
Wherein, nickel source described in step (2) is the one or more in nickel acetate, nickel nitrate or nickel chloride, preferably second
Sour nickel；The manganese source is the one or more in simple substance manganese powder, manganese acetate, manganese nitrate or manganese chloride, preferably simple substance manganese powder.Institute
Lithium source is stated as the one or more in lithium acetate, lithium nitrate or lithium chloride, preferably lithium acetate.Phosphorus source is phosphoric acid hydrogen two
One or more in ammonium, ammonium dihydrogen phosphate or ammonium phosphate, preferably diammonium hydrogen phosphate.
Wherein, the mol ratio of the citric acid and manganese source is (6~12):4.5, be preferably (6~10):4.5；
And/or
According to citric acid, manganese, nickel, lithium, phosphorus mole meter, the citric acid and manganese source, nickel source, mole of lithium source and phosphorus source
Than for (6~12):(4~4.5):(1~2):3.15:(0.01~0.21).
Further, the citric acid and the mol ratio of manganese source, nickel source, lithium source and phosphorus source are (6~10):4.3125:
1.5:3.15:(0.1~0.21), more preferably (6~10):4.3125:1.5:3.15:0.15.
Alternatively, the mol ratio of the citric acid in the aqueous solution of citric acid and manganese source, nickel source, lithium source and phosphorus source for (6~
12):(4~4.5):1.5:3.15:(0~0.21), 8:4.3125:1.5:3.15:0.15.Such as can be 6:4:1.5:3.15:
0.21、8:4:1.5:3.15:0.21、10:4:1.5:3.15:0.21、12:4:1.5:3.15:0.21、6:4.2375:1.5:
3.15:0.15、8:4.2375:1.5:3.15:0.15、10:4.2375:1.5:3.15:0.15、12:4.2375:1.5:3.15:
0.15、6:4.3125:1.5:3.15:0.15、8:4.3125:1.5:3.15:0.15、10:4.3125:1.5:3.15:0.15、
12:4.3125:1.5:3.15:0.15、6:4.3875:1.5:3.15:0.15、8:4.3875:1.5:3.15:0.15、10:
4.3875:1.5:3.15:0.15、12:4.3875:1.5:3.15:0.15 etc., be preferably (6~10):4.3125:1.5:3.15:
0.15, the present invention has found that mol ratio is 8 by lot of experiments:4.3125:1.5:3.15:Gained P non-equivalent doping when 0.15
Battery made from nickel lithium manganate cathode material has more preferable high rate performance and cycle performance, therefore preferred mol ratio is 8:
4.3125:1.5:3.15:0.15。
Optimal technical scheme of the present invention also includes, and the concentration of the aqueous solution of citric acid is 0.7~1.3mol/ in step (1)
L.Stirring is magnetic agitation described in step (1), and the temperature of stirring is preferably 10~40 DEG C；
The temperature stirred described in step (2) is 10~40 DEG C, and the time of stirring is 1~10h, preferably 5~6h；
Stirring is stirred for constant temperature described in step (3), and the temperature of constant temperature stirring is 60~90 DEG C.
Wherein, in step (4), the temperature of the predecomposition is 180~350 DEG C, and the time of predecomposition is 2~6h.
Before predecomposition product is heat-treated, first predecomposition product is ground.
Wherein, in step (5), the heat treatment is carried out in air atmosphere；
The temperature of first step sintering is 550~750 DEG C, preferably 650 DEG C；The time of first step sintering is 5~15h,
The temperature of second step sintering is 850~950 DEG C, preferably 900 DEG C；The time of second step sintering is 1~5h.
The Modified Nickel lithium manganate material that the method for the invention is prepared.
Purposes of the Modified Nickel lithium manganate material as anode material for lithium-ion batteries.
The beneficial effects of the present invention are：
(1) the invention provides a kind of method that nickel ion doped is modified using nonmetal doping, methods described is simple,
Efficiency high, cost are low, energy consumption is small and are easy to industrialization large-scale production.
(2) the nickel ion doped tap density height for the non-equivalent doping vario-properties of P that the present invention is prepared, purity are high and without miscellaneous
Phase, as anode material for lithium-ion batteries, there is good high rate performance and cycle performance.Under 1C discharge-rate, for the first time
Capacity reaches 119mAh/g；Under 40C discharge-rate, first capacity reaches 98mAh/g；By 1000 circulations under 1C multiplying power
Capability retention about 95% afterwards, 80% is still up to by 1600 circulation volume conservation rates；Followed under 10C multiplying powers by 1000 times
Ring capability retention is about 93%, and 87% is still up to by 1600 circulation volume conservation rates.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the nickel ion doped of the non-equivalent doping vario-properties of P resulting in the embodiment of the present invention 1.
Fig. 2 (a), Fig. 2 (b), Fig. 2 (c) are respectively the nickel ion doped of the non-equivalent doping vario-properties of P in the embodiment of the present invention 1
Scanning electron microscope (SEM) photograph under different amplification.
Fig. 3 (a), Fig. 3 (b) are the multiplying power of the nickel ion doped of the non-equivalent doping vario-properties of P resulting in the embodiment of the present invention 1
Cycle performance and voltage change under different multiplying is shown respectively in performance curve, Fig. 3 (a), Fig. 3 (b).
Fig. 4 (a), (b) are the nickel ion doped room temperature condition of the non-equivalent doping vario-properties of P resulting in the embodiment of the present invention 1
Lower 1C and 10C cycle performance curves.
Embodiment
Multifunctional nano drug-loading system and its performance etc. are illustrated below by way of specific embodiment.
Material in example below is directly to be prepared according to existing method, or is directly bought from the market.
Experimental example 1
0.08mol citric acid is incorporated in 100ml deionized water, sequentially added after citric acid dissolving
0.043125mol simple substance manganese powder, 0.015mol nickel acetate, 0.0315mol lithium acetate and 0.0015mol phosphoric acid hydrogen two
Ammonium；Magnetic stirs 5 hours at ambient temperature in above-mentioned clear solution；By mixed liquor, magnetic agitation is steamed under 80 DEG C of constant temperatures
It is dry, obtain presoma；By above-mentioned presoma at 230 DEG C predecomposition 4h, gained predecomposition product is ground to obtain grinding product；
By the grinding product, two-step thermal processing, two-step thermal processing condition are respectively 650 DEG C of temperature, time under the conditions of air atmosphere
10h and 900 DEG C of temperature, time 2h, then furnace cooling obtain the nickel ion doped lithium ion battery of the non-equivalent doping of high performance P
Positive electrode.
Referring to Fig. 1, X-ray powder diffraction analysis shows, product is the pure phase nickel ion doped that space group is Fd3m, and it is crystallized
Degree is high.
Referring to Fig. 2 (a), Fig. 2 (b), Fig. 2 (c), learnt from scanning electron microscope analysis, the primary granule of product is not
Part be present between 0.5~2 μm, between primary granule and reunite in regular polyhedron, particle diameter.
Using product as positive electrode, experiment fastening lithium ionic cell, its times are assembled into the glove box of argon gas protection
Discharge curve under rate performance and different multiplying is shown in Fig. 3 (a) and Fig. 3 (b).It is first to hold under 1C discharge-rate
Amount reaches 119mAh/g；Under 40C discharge-rate, first capacity reaches 98mAh/g；Under 1C multiplying power after 1000 circulations
Capability retention about 95%, 80% (Fig. 4 (a)) is still up to by 1600 circulation volume conservation rates；Pass through under 10C multiplying powers
1000 circulation volume conservation rates are about 93% (Fig. 4 (b)), and 87% is still up to by 1600 circulation volume conservation rates.More than
Data show that the nickel ion doped of the non-equivalent doping of synthesized P is assembled into battery as positive electrode has excellent electrochemistry
Performance.
Embodiment 2
0.06mol citric acid is incorporated in 100ml deionized water, sequentially added after citric acid dissolving
0.043125mol simple substance manganese powder, 0.015mol nickel acetate, 0.0315mol lithium acetate and 0.0015mol phosphoric acid hydrogen two
Ammonium；Magnetic stirs 5 hours at ambient temperature in above-mentioned clear solution；By mixed liquor, magnetic agitation is steamed under 80 DEG C of constant temperatures
It is dry, obtain presoma；By above-mentioned presoma at 230 DEG C predecomposition 4h, the predecomposition product is ground to obtain grinding product；
By the grinding product under the conditions of air atmosphere two-step thermal processing, treatment conditions are 650 DEG C of 10h and 900 DEG C of 2h, then with stove
Cooling obtains the nickel ion doped anode material for lithium-ion batteries of the non-equivalent doping of high performance P.
X-ray powder diffraction analysis shows, product are the pure phase nickel ion dopeds that space group is Fd3m, and its crystallinity is high；From
Scanning electron microscope analysis learn that the primary granule of product is irregular polyhedron, and particle diameter is primary between 0.5~2 μm
There is part between particle to reunite.Using product as positive electrode, experiment button lithium is assembled into the glove box of argon gas protection
Ion battery, charge and discharge cycles are carried out between 3.5~4.95V with different multiplying powers.Under 1C discharge-rate, first capacity reaches
110mAh/g；Under 40C discharge-rate, first capacity reaches 80mAh/g；Kept under 10C multiplying powers by 600 circulation volumes
Rate is about 80%.
Embodiment 3
0.10mol citric acid is incorporated in 100ml deionized water, sequentially added after citric acid dissolving
0.043125mol simple substance manganese powder, 0.015mol nickel acetate, 0.0315mol lithium acetate and 0.0015mol phosphoric acid hydrogen two
Ammonium；Magnetic stirs 5 hours at ambient temperature in above-mentioned clear solution；By mixed liquor, magnetic agitation is steamed under 80 DEG C of constant temperatures
It is dry, obtain presoma；By above-mentioned presoma at 230 DEG C predecomposition 4h, the predecomposition product is ground to obtain grinding product；
By the grinding product under the conditions of air atmosphere two-step thermal processing, treatment conditions are 650 DEG C of 10h and 900 DEG C of 2h, then with stove
Cooling obtains the nickel ion doped anode material for lithium-ion batteries of the non-equivalent doping of high performance P.
X-ray powder diffraction analysis shows, product are the pure phase nickel ion dopeds that space group is Fd3m, and its crystallinity is high；From
Scanning electron microscope analysis learn that the primary granule of product is irregular polyhedron, and particle diameter is primary between 0.5~2 μm
There is part between particle to reunite.Using product as positive electrode, experiment button lithium is assembled into the glove box of argon gas protection
Ion battery, charge and discharge cycles are carried out between 3.5~4.95V with different multiplying powers.Under 1C discharge-rate, first capacity reaches
105mAh/g；Under 40C discharge-rate, first capacity reaches 75mAh/g；Kept under 10C multiplying powers by 600 circulation volumes
Rate is about 79%.
Embodiment 4
0.08mol citric acid is incorporated in 100ml deionized water, sequentially added after citric acid dissolving
0.042375mol simple substance manganese powder, 0.015mol nickel acetate, 0.0315mol lithium acetate and 0.0015mol phosphoric acid hydrogen two
Ammonium；Magnetic stirs 5 hours at ambient temperature in above-mentioned clear solution；By mixed liquor, magnetic agitation is steamed under 80 DEG C of constant temperatures
It is dry, obtain presoma；By above-mentioned presoma at 230 DEG C predecomposition 4h, the predecomposition product is ground to obtain grinding product；
By the grinding product, two-step thermal processing, two-step thermal processing condition are respectively 650 DEG C 10h and 900 DEG C under the conditions of air atmosphere
2h, then furnace cooling obtain the nickel ion doped anode material for lithium-ion batteries of the non-equivalent doping of high performance P.
X-ray powder diffraction analysis shows, product are the pure phase nickel ion dopeds that space group is Fd3m, and its crystallinity is high；From
Scanning electron microscope analysis learn that the primary granule of product is irregular polyhedron, and particle diameter is primary between 0.5~2 μm
There is part between particle to reunite.Using product as positive electrode, experiment button lithium is assembled into the glove box of argon gas protection
Ion battery, charge and discharge cycles are carried out between 3.5~4.95V with different multiplying powers.Under 1C discharge-rate, first capacity reaches
114mAh/g；Under 40C discharge-rate, first capacity reaches 75mAh/g；Under 1C multiplying power by 1000 times circulation after capacity
Conservation rate about 76%；By 1000 circulation volume conservation rates it is about 91% under 10C multiplying powers.
Embodiment 5
0.10mol citric acid is incorporated in 100ml deionized water, sequentially added after citric acid dissolving
0.042375mol simple substance manganese powder, 0.015mol nickel acetate, 0.0315mol lithium acetate and 0.0015mol phosphoric acid hydrogen two
Ammonium；Magnetic stirs 5 hours at ambient temperature in above-mentioned clear solution；By mixed liquor, magnetic agitation is steamed under 80 DEG C of constant temperatures
It is dry, obtain presoma；By above-mentioned presoma at 230 DEG C predecomposition 4h, gained predecomposition product is ground to obtain grinding product；
By the grinding product, two-step thermal processing, treatment conditions are respectively 650 DEG C of temperature, time 10h and temperature under the conditions of air atmosphere
900 DEG C, time 2h are spent, then furnace cooling obtains the nickel ion doped lithium ion cell positive material of the non-equivalent doping of high performance P
Material.
X-ray powder diffraction analysis shows, product are the pure phase nickel ion dopeds that space group is Fd3m, and its crystallinity is high；From
Scanning electron microscope analysis learn that the primary granule of product is irregular polyhedron, and particle diameter is primary between 0.5~2 μm
There is part between particle to reunite.Using product as positive electrode, experiment button lithium is assembled into the glove box of argon gas protection
Ion battery, charge and discharge cycles are carried out between 3.5~4.95V with different multiplying powers.Under 1C discharge-rate, first capacity reaches
110mAh/g；Under 40C discharge-rate, first capacity reaches 73mAh/g；Kept under 10C multiplying powers by 600 circulation volumes
Rate is about 85%.
Embodiment 6
0.08mol citric acid is incorporated in 100ml deionized water, sequentially added after citric acid dissolving
0.043875mol simple substance manganese powder, 0.015mol nickel acetate, 0.0315mol lithium acetate and 0.0015mol phosphoric acid hydrogen two
Ammonium；Magnetic stirs 5 hours above-mentioned clear solution at ambient temperature；By mixed liquor, magnetic agitation is evaporated under 80 DEG C of constant temperatures,
Obtain presoma；By above-mentioned presoma at 230 DEG C predecomposition 4h, gained predecomposition product is ground to obtain grinding product；Will
Grinding product two-step thermal processing under the conditions of air atmosphere, the heat treatment condition of two steps is respectively 650 DEG C × 10h and 900
DEG C × 2h, then furnace cooling obtains the nickel ion doped anode material for lithium-ion batteries of high performance P non-equivalent doping.
X-ray powder diffraction analysis shows, product are the pure phase nickel ion dopeds that space group is Fd3m, and its crystallinity is high；From
Scanning electron microscope analysis learn that the primary granule of product is irregular polyhedron, and particle diameter is primary between 0.5~2 μm
There is part between particle to reunite.Using product as positive electrode, experiment button lithium is assembled into the glove box of argon gas protection
Ion battery, charge and discharge cycles are carried out between 3.5~4.95V with different multiplying powers.Under 1C discharge-rate, first capacity reaches
100mAh/g；Under 40C discharge-rate, first capacity reaches 67mAh/g；Under 1C multiplying power by 1000 times circulation after capacity
Conservation rate about 68%；By 1000 circulation volume conservation rates it is about 87% under 10C multiplying powers.
Embodiment 7
0.06mol citric acid is incorporated in 100ml deionized water, sequentially added after citric acid dissolving
0.043875mol simple substance manganese powder, 0.015mol nickel acetate, 0.0315mol lithium acetate and 0.0015mol phosphoric acid hydrogen two
Ammonium；Magnetic stirs 5 hours at ambient temperature in above-mentioned clear solution；By mixed liquor, magnetic agitation is steamed under 80 DEG C of constant temperatures
It is dry, obtain presoma；By above-mentioned presoma at 230 DEG C predecomposition 4h, the predecomposition product is ground to obtain grinding product；
By the grinding product, two-step thermal processing, treatment conditions are 650 DEG C × 10h and 900 DEG C × 2h under the conditions of air atmosphere, then
Furnace cooling obtains the nickel ion doped anode material for lithium-ion batteries of the non-equivalent doping of high performance P.
X-ray powder diffraction analysis shows, product are the pure phase nickel ion dopeds that space group is Fd3m, and its crystallinity is high；From
Scanning electron microscope analysis learn that the primary granule of product is irregular polyhedron, and particle diameter is primary between 0.5~2 μm
There is part between particle to reunite.Using product as positive electrode, experiment button lithium is assembled into the glove box of argon gas protection
Ion battery, charge and discharge cycles are carried out between 3.5~4.95V with different multiplying powers.Under 1C discharge-rate, first capacity reaches
102mAh/g；Under 40C discharge-rate, first capacity reaches 65mAh/g；Under 1C multiplying power by 1000 times circulation after capacity
Conservation rate about 65%；By 1000 circulation volume conservation rates it is about 80% under 10C multiplying powers.
Comparative example 1
0.08mol citric acid is incorporated in 100ml deionized water, sequentially added after citric acid dissolving
0.045mol simple substance manganese powder, 0.015mol nickel acetate and 0.0315mol lithium acetate, other preparation methods and condition and reality
It is identical to apply example 1.
The nickel ion doped LiNi that this comparative example is prepared0.5Mn1.5O4, using product as positive electrode, argon gas protection
Experiment fastening lithium ionic cell is assembled into glove box, charge and discharge cycles, 1C are carried out between 3.5~4.95V with different multiplying powers
Initial discharge capacity is 118mAh/g, and 40C initial discharges capacity is 67mAh/g；At ambient temperature, 1C is by 1000 circulations
Capability retention is 42%；By 1000 circulation volume conservation rates it is about 51% under 10C multiplying powers.
Embodiment above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered
Row limits, on the premise of design spirit of the present invention is not departed from, technical side of this area ordinary skill technical staff to the present invention
The all variations and modifications that case is made, it all should fall into the protection domain of claims of the present invention determination.
Claims (10)
- A kind of 1. method of the non-equivalent substitution Mn doping vario-property nickel ion dopeds of P, it is characterised in that non-etc. using nonmetalloid P Measure and realized for a small amount of Mn to LiNi0.5Mn1.5O4Doping vario-property, by introducing a small amount of room in 16d positions to adjust material The content of oxygen defect in material, optimize orderly, unordered spinel structure ratio in material, realize the optimization of material combination property； In preparation process, citric acid is first dissolved in appropriate deionized water, lithium source, manganese source, nickel source and phosphorus source is then sequentially added and obtains To mixed solution, heat and stir to mixed solution and be evaporated, then through predecomposition and heat treatment, produce the nickel manganese of the non-equivalent doping of P Sour lithium.
- 2. according to the method for claim 1, it is characterised in that including step：(1) citric acid is dissolved in deionized water, obtains clear solution；(2) lithium source, manganese source, nickel source and phosphorus source are added in the clear solution obtained to step (1), stirring, obtains mixed solution；(3) mixed solution that step (2) obtains is stirred, is evaporated to mixed solution, obtains xerogel；(4) xerogel for obtaining step (3) carries out predecomposition, obtains predecomposition product；(5) the predecomposition product for obtaining step (4) carries out the heat treatment of two-step sintering, obtains the nickel mangaic acid of the non-equivalent doping of P Lithium.
- 3. according to the method for claim 1, it is characterised in that nickel source described in step (2) is nickel acetate, nickel nitrate or chlorine Change the one or more in nickel；The manganese source be simple substance manganese powder, manganese acetate, manganese nitrate or manganese chloride in one or more, institute Lithium source is stated as the one or more in lithium acetate, lithium nitrate or lithium chloride, elects lithium acetate as.Phosphorus source be diammonium hydrogen phosphate, One or more in ammonium dihydrogen phosphate or ammonium phosphate.
- 4. according to the method described in any one of claims 1 to 3, it is characterised in that the mol ratio of the citric acid and manganese source is (6~12):4.5, be preferably (6~10):4.5；And/orAccording to citric acid, manganese, nickel, lithium, phosphorus mole meter, the citric acid and the mol ratio of manganese source, nickel source, lithium source and phosphorus source are (6~12):(4~4.5):(1~2):3.15:(0.01~0.21).
- 5. according to the method for claim 4, it is characterised in that the citric acid rubs with manganese source, nickel source, lithium source and phosphorus source Your ratio is (6~10):4.3125:1.5:3.15:(0.1~0.21), it is preferably (6~10):4.3125:1.5:3.15:0.15.
- 6. according to the method for claim 2, it is characterised in that in step (1) concentration of the aqueous solution of citric acid be 0.7~ 1.3mol/L；The temperature stirred described in step (2) is 10~40 DEG C, and the time of stirring is 1~10h,Stirring is stirred for constant temperature described in step (3), and the temperature of constant temperature stirring is 60~90 DEG C.
- 7. according to the method for claim 2, it is characterised in that in step (4), the temperature of the predecomposition is 180~350 DEG C, the time of predecomposition is 2~6h,Before predecomposition product is heat-treated, first predecomposition product is ground.
- 8. according to the method described in any one of claim 2~7, it is characterised in that in step (5), the heat treatment is in air Carried out under atmosphere；The temperature of first step sintering is 550~750 DEG C, and the time of first step sintering is 5~15h,The temperature of second step sintering is 850~950 DEG C, and the time of second step sintering is 1~5h.
- 9. the Modified Nickel lithium manganate material that any one of claim 1~8 methods described is prepared.
- 10. purposes of the Modified Nickel lithium manganate material as anode material for lithium-ion batteries described in claim 9.
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| CN109244390A (en) * | 2018-08-21 | 2019-01-18 | 哈尔滨工业大学 | A kind of lithium ion battery phosphorus doping lithium-rich manganese-based anode material and preparation method thereof |
| CN111916725A (en) * | 2019-05-08 | 2020-11-10 | 中国石油化工股份有限公司 | Phosphorus-doped lithium battery high-nickel positive electrode material and preparation process thereof |
| CN113795953A (en) * | 2021-02-03 | 2021-12-14 | 宁德新能源科技有限公司 | Positive plate, electrochemical device comprising same and electronic device |
| CN117457892A (en) * | 2023-12-22 | 2024-01-26 | 宁波容百新能源科技股份有限公司 | Positive electrode active material, preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244390A (en) * | 2018-08-21 | 2019-01-18 | 哈尔滨工业大学 | A kind of lithium ion battery phosphorus doping lithium-rich manganese-based anode material and preparation method thereof |
| CN109244390B (en) * | 2018-08-21 | 2021-04-13 | 哈尔滨工业大学 | Phosphorus-doped lithium-rich manganese-based positive electrode material for lithium ion battery and preparation method thereof |
| CN111916725A (en) * | 2019-05-08 | 2020-11-10 | 中国石油化工股份有限公司 | Phosphorus-doped lithium battery high-nickel positive electrode material and preparation process thereof |
| CN113795953A (en) * | 2021-02-03 | 2021-12-14 | 宁德新能源科技有限公司 | Positive plate, electrochemical device comprising same and electronic device |
| WO2022165676A1 (en) * | 2021-02-03 | 2022-08-11 | 宁德新能源科技有限公司 | Positive plate and electrochemical apparatus including positive plate, and electronic apparatus |
| CN117457892A (en) * | 2023-12-22 | 2024-01-26 | 宁波容百新能源科技股份有限公司 | Positive electrode active material, preparation method and application thereof |
| CN117457892B (en) * | 2023-12-22 | 2024-04-12 | 宁波容百新能源科技股份有限公司 | Positive electrode active material, preparation method and application thereof |
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| CN107611422B (en) | 2019-12-31 |
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