CN105576236A - Lithium ion battery 442 ternary anode modified material and preparing method thereof - Google Patents
Lithium ion battery 442 ternary anode modified material and preparing method thereof Download PDFInfo
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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
- H01M4/48—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
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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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- H01M4/48—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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Abstract
The invention relates to a lithium ion battery 442 ternary anode modified material. The lithium ion battery 442 ternary anode modified material comprises an anode material, wherein the outer layer of the anode material is wrapped in a layer of clad material, and the mass ratio of the clad material to the anode material is 0-5 wt%. The general chemical formula of the anode material is Li(Ni0.4Co0.2Mn0.4)1-xMxO2-yNy, wherein M is Ti, Mg, Al or Cr, N is F, Cl or Br, 0<x<=0.10, and 0<y<=0.10. The clad material is TiO2, Al2O3 or FePO4. The lithium ion battery 442 ternary anode modified material is prepared in the way of obtaining gel by means of raw materials with the sol-gel method, conducting heating and drying, then conducting fire-grinding twice to obtain the anode material, suspending the anode material and the clad material in deionized water, conducting constant-temperature stirring, then conducting standing, filtering, washing and drying, and conducting calcination to obtain the lithium ion battery 442 ternary anode modified material. The preparing method is simple and easy to operate, the particle size distribution of the prepared ternary anode modified material is uniform, the crystallinity degree is high, the surface is smooth, the particle dispersion degree is high, and the rate capability and cycle performance of the material are improved.
Description
Technical field
The present invention relates to a kind of lithium ion battery 442 type tertiary cathode material modified and preparation method thereof, belong to anode material for lithium-ion batteries technical field.
Background technology
In the element of lithium ion battery, positive electrode all occupies leading factor in price and aspect of performance.With regard to present development degree, the development speed of positive electrode also more than negative material and electrolyte is slow, the further improvement of performance of lithium ion battery and fail safe more it is desirable that positive electrode circulation, the improving constantly of high rate performance and thermal stability.Tertiary cathode material is LiCoO
2/ LiNiO
2/ LiMn
2o
4eutectic system, this eutectic system has had LiCoO concurrently
2, LiNiO
2, LiMn
2o
4the feature of three class materials, this material is a kind of advanced composite material (ACM) containing nickel, cobalt, manganese three kinds of elements, and ternary material exists obvious element cooperative effect, and chemical property is better than any one single combination of compounds.
As (442) type ternary material LiNi a kind of in ternary system
0.4co
0.2mn
0.4o
2, with traditional (333) type LiNi
1/3mn
1/3co
1/3o
2material is compared, and the content of Co reduces, and the production cost of material can be made to reduce, and manufacture of materials is more friendly to environment with use procedure simultaneously.The content of Ni is higher, contributes to material and obtains higher discharge capacity.Meanwhile, contribute the content of maximum Mn to increase to material safety and stability, material circulation and fail safe can be made better, be more suitable for practical application, thus LiNi
0.4co
0.2mn
0.4o
2it is a kind of tertiary cathode material having more researching value.
And with regard to the requirement of commercial applications, LiNi
0.4co
0.2mn
0.4o
2tap density that what positive electrode needed to improve is, can the charging and discharging capabilities of force density, circulation ability and large multiplying power.For current LiNi
0.4co
0.2mn
0.4o
2the deficiency that tertiary cathode material remains, researchers mainly carry out part doping or surface coating modification to material, doping vario-property is mainly by other metal ions close with bulk transition metal ionic radius that partly adulterate in positive electrode, or the anion such as part doped F, Cl or Br make material structure more stable to reach, the object that cycle performance is more outstanding; Coated this modified method adheres to the material of one deck stable chemical nature on the surface at positive electrode, material is effectively avoided to contact with the direct of electrolyte, suppress the interaction between them by such mode, ensure material structure complete and stable in cyclic process.In addition, coating modification suitably can also improve conductivity and the tap density of positive electrode, make coated after positive electrode high rate performance better and be conducive to industrial processes.Two kinds of modified methods combine, to LiNi by this patent
0.4co
0.2mn
0.4o
2positive electrode carries out adulterating or coated modified synergic.
Summary of the invention
The object of the invention is to solve the problem, provide a kind of preparation method simple lithium ion battery 442 type tertiary cathode material modified and preparation method thereof, the positive electrode even particle size distribution prepared, structure is more stable, material high rate performance and cycle performance better.
The present invention adopts following technical scheme: a kind of lithium ion battery 442 type tertiary cathode is material modified, comprise the positive electrode of doping vario-property, the outer layer covers of the positive electrode of described doping vario-property has one deck clad material, the quality of described clad material is the 1-5wt% of the positive electrode of doping vario-property, and the chemical general formula of the positive electrode of described doping vario-property is Li (Ni
0.4co
0.2mn
0.4)
1-xm
xo
2-yn
y, wherein, M is Ti, Mg, Al or Cr; N is F, Cl or Br, 0 < x≤0.10,0 < y≤0.10, and described clad material is TiO
2, A1
2o
3or FePO
4.
The preparation method that lithium ion battery 442 type tertiary cathode is material modified, comprises the steps:
(1) by abundant mixing soluble in water to water miscible lithium source, nickel source, manganese source, cobalt source, M salt, N salt and citric acid, then ammoniacal liquor adjust ph to 7 ~ 8 are used;
(2) the solution agitating heating at 60 ~ 100 DEG C step (1) obtained, obtains gelinite;
(3) by drying at step (2) gained gelinite 80 ~ 150 DEG C 8 ~ 15 hours, xerogel body is obtained;
(4) by xerogel body 300 ~ 600 DEG C of pre-calcination process 4 ~ 8 hours, naturally cool to grinding at room temperature and obtain presoma;
(5) presoma that step (4) obtains to be placed under 700 ~ 1000 DEG C of conditions roasting 10 ~ 20 hours, continues the positive electrode that grinding obtains doping vario-property after cooling;
(6) by the quality of clad material be doping vario-property positive electrode 1-5wt% weigh clad material, clad material is TiO
2, A1
2o
3or FePO
4;
(7) positive electrode of the above-mentioned doping vario-property prepared and clad material being scattered in the positive electrode making doping vario-property in water or ethanol and clad material dissolves completely, vigorous stirring at 40 ~ 80 DEG C, and regulate pH 9 ~ 10, until solvent volatilizees completely, stirring terminates to adopt quantitative filter paper to filter in latter standing 1 ~ 2 hour, and after spending deionized water 1 ~ 2 time under 80 ~ 85 DEG C of conditions dry 12 ~ 20 hours, finally namely obtain end product at 400 ~ 500 DEG C of calcining 5 ~ 10h.
Further, described lithium source, nickel source, manganese source, cobalt source, M salt, N salt are (1-y) according to the mol ratio of lithium, nickel, manganese, cobalt, M, N: (0.4-x): (0.4-x): (0.2-x): x:y adds, wherein 0 < x≤0.10,0 < y≤0.10.
Further, the integral molar quantity of described nickel salt, cobalt salt and manganese salt and the mol ratio of citric acid are 1:1 ~ 1:2.
Further, described lithium source is LiNO
3, CH
3one or more in COOLi, LiOH.
Further, described nickel source is Ni (NO
3)
2, Ni (CH
3cOO)
2, NiSO
4in one or more.
Further, described manganese source is Mn (NO
3)
2, Mn (CH
3cOO)
2, MnSO
4in one or more.
Further, described cobalt source is Co (NO
3)
2, Co (CH
3cOO)
2, CoSO
4in one or more
Further, described M salt is Mg (NO
3)
2, C
16h
36o
4ti, Al (NO
3)
3or Cr (NO
3)
3in one.
Further, described N salt is the one in LiCl, LiF, LiBr.
Preparation method of the present invention is simple, step is easy to operation, the positive electrode even particle size distribution prepared, degree of crystallinity is high, smooth surface, and particle dispersion is good, because anion and cationic doping vario-property make material structure more stable, and the existence of clad material inhibits the generation of material surface and electrolyte interface side reaction, reduce the impedance in cyclic process, improve Li
+diffusion rate, make material surface Li
+it is easier to deviate from embedding, doping serves with the comprehensive function of coating modification and improves material high rate performance and cycle performance, and doping is cheap with the cost of material needed for coating modification, reduce further the cost needed for positive electrode production, be conducive to advancing commercial process.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of positive electrode prepared by comparative example and embodiment 2,3,5.
Fig. 2 is the scanning electron microscope (SEM) photograph of positive electrode prepared by comparative example and embodiment 2,3,5.
Fig. 3 is positive electrode prepared by comparative example and embodiment 2,3,5, and first charge-discharge curve chart during normal temperature under 0.2C electric current, discharge voltage range is 2.5-4.6V.
Fig. 4 is positive electrode prepared by comparative example and embodiment 2,3,5, and cyclic curve figure during normal temperature under 0.2C electric current, charging/discharging voltage scope is 2.5-4.6V.
Fig. 5 is positive electrode prepared by comparative example and embodiment 2,3,5, and the cyclic curve figure when normal temperature under different multiplying, charging/discharging voltage scope is 2.5-4.6V.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Comparative example: unmodified LiNi
0.4co
0.2mn
0.4o
2the preparation of positive electrode.
Analytically pure CH is taken according to stoichiometric proportion (1.05:0.4:0.2:0.4)
3cOOLi, Ni (CH
3cOO)
2, Co (CH
3cOO)
2, Mn (CH
3cOO)
2fully dissolve with deionized water respectively, add citric acid solution, the addition of citric acid solution equals the mole sum of transition metal ions, mix rear concentrated ammonia liquor and solution ph is adjusted to 7.5,80 DEG C of heating water baths stir, make the abundant complexing of various ion, and make moisture be evaporated to formation darkviolet gel; By gel under 120 DEG C of conditions dry 10 hours, and preliminary treatment 6 hours at being placed on 500 DEG C, grinding after cooling, then within 20 hours, obtain LiNi in 850 DEG C of roastings
0.4co
0.2mn
0.4o
2positive electrode.
Embodiment 1: the preparation method that a kind of lithium ion battery 442 type tertiary cathode is material modified, comprises the steps:
(1) analytically pure CH is taken according to stoichiometric proportion (1.02:0.388:0.194:0.388:0.03:0.03)
3cOOLi2H
2o, Ni (CH
3cOO)
24H
2o, Co (CH
3cOO)
24H
2o, Mn (CH
3cOO) 4H
2o, Mg (NO
3)
26H
2o, LiF, complete with deionized water dissolving respectively, add citric acid solution, the addition of citric acid solution equals the mole sum of transition metal ions, mixes rear concentrated ammonia liquor and pH value is adjusted to 7;
(2) mixed solution that step (1) obtains is heated with transpiring moisture in the water-bath of 60 DEG C, and constantly stir, obtain gelinite;
(3) dried in air dry oven by gelinite, bake out temperature is 80 DEG C, and drying time is 8 hours, obtains xerogel body;
(4) gelinite of drying is carried out pre-burning, calcined temperature is 300 DEG C, and burn-in time is 8 hours, obtains presoma; Presoma grinds after naturally cooling to room temperature, and calcined at 700 DEG C by the presoma after grinding, calcination time is 10 hours, again grinds after naturally cooling to room temperature after calcining, namely obtains the positive electrode Li (Ni of doping vario-property
0.4co
0.2mn
0.4)
0.97mg
0.03o
1.97f
0.03.
(5) by the above-mentioned doping vario-property positive electrode for preparing and the mass fraction clad material TiO than 1.0wt%
2in dispersion amount of alcohol solvent, vigorous stirring at 40 DEG C, and regulate PH 9, until solvent volatilizees completely, stirring terminates to adopt quantitative filter paper to filter in latter standing 1 hour, and after spending deionized water 1 time under 80 DEG C of conditions dry 20 hours, namely last 400 DEG C of calcining 10h obtain end product Surface coating 1.0wt%TiO
2li (Ni
0.4co
0.2mn
0.4)
0.97mg
0.03o
1.97f
0.03.
Embodiment 2: the preparation method that a kind of lithium ion battery 442 type tertiary cathode is material modified, comprises the steps:
(1) analytically pure LiNO is taken according to stoichiometric proportion (1.00:0.38:0.19:0.38:0.05:0.05)
3, Ni (NO
3)
26H
2o, Co (NO
3)
26H
2o, Mn (NO
3)
24H
2o, C
16h
36o
4ti, LiCl, complete with deionized water dissolving respectively, add citric acid solution, the addition of citric acid solution equals the mole sum of transition metal ions, mixes rear concentrated ammonia liquor and pH value is adjusted to 7.5;
(2) mixed solution that step (1) obtains is heated with transpiring moisture in the water-bath of 80 DEG C, and constantly stir, obtain gelinite;
(3) dried in air dry oven by gelinite, bake out temperature is 100 DEG C, and drying time is 10 hours, obtains xerogel body;
(4) gelinite of drying is carried out pre-burning, calcined temperature is 400 DEG C, and burn-in time is 5 hours, obtains presoma; Presoma grinds after naturally cooling to room temperature, and calcined at 850 DEG C by the presoma after grinding, calcination time is 15 hours, again grinds after naturally cooling to room temperature after calcining, namely obtains the positive electrode Li (Ni of doping vario-property
0.4co
0.2mn
0.4)
0.95ti
0.05o
1.95cl
0.05.
(5) by the positive electrode of the above-mentioned doping vario-property prepared and the mass fraction clad material A1 than 2.0wt%
2o
3be scattered in appropriate solvent, vigorous stirring at 60 DEG C, and regulate PH about 9, until solvent volatilizees completely.Stirring terminates to leave standstill 2 hours and adopt quantitative filter paper to filter afterwards, and after spending deionized water 2 times under 85 DEG C of conditions dry 12 hours, namely last 450 DEG C of calcining 8h obtain end product Surface coating 2.0wt%A1
2o
3li (Ni
0.4co
0.2mn
0.4)
0.95ti
0.05o
1.95cl
0.05.
Embodiment 3: the preparation method that a kind of lithium ion battery 442 type tertiary cathode is material modified, comprises the steps:
(1) analytically pure LiOHH is taken according to stoichiometric proportion (0.95:0.36:0.18:0.36:0.1:0.1)
2o, NiSO
46H
2o, CoSO
47H
2o, MnSO
4h
2o, Al (NO
3)
3, LiBr, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mixes rear concentrated ammonia liquor and pH value is adjusted to about 8;
(2) mixed solution that step (1) obtains is heated with transpiring moisture in the water-bath of 90 DEG C, and constantly stir, obtain gelinite;
(3) dried in air dry oven by gelinite, bake out temperature is 120 DEG C, and drying time is 12 hours, obtains xerogel body;
(4) gelinite of drying is carried out pre-burning, calcined temperature is 500 DEG C, and burn-in time is 6 hours, obtains presoma; Presoma grinds after naturally cooling to room temperature, and calcined at 900 DEG C by the presoma after grinding, calcination time is 18 hours, again grinds after naturally cooling to room temperature after calcining, namely obtains the positive electrode Li (Ni of doping vario-property
0.4co
0.2mn
0.4)
0.9al
0.1o
1.9br
0.1.
(5) by the positive electrode of the above-mentioned doping vario-property prepared and the mass fraction clad material FePO than 3.0wt%
4be scattered in appropriate solvent, vigorous stirring at 80 DEG C, and regulate PH about 9, until solvent volatilizees completely.Stirring terminates to leave standstill 1.5 hours and adopt quantitative filter paper to filter afterwards, and after spending deionized water 2 times under 80 DEG C of conditions dry 15 hours, namely last 500 DEG C of calcining 5h obtain end product Surface coating 3.0wt%FePO
4li (Ni
0.4co
0.2mn
0.4)
0.9al
0.1o
1.9br
0.1.
Embodiment 4: the preparation method that a kind of lithium ion battery 442 type tertiary cathode is material modified, comprises the steps:
(1) analytically pure LiNO is taken according to stoichiometric proportion (1.00:0.38:0.19:0.38:0.05:0.05)
3, Ni (NO
3)
26H
2o, Co (NO
3)
26H
2o, Mn (NO
3)
24H
2o, Cr (NO
3)
34H
2o, LiF, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mixes rear concentrated ammonia liquor and pH value is adjusted to about 7.0;
(2) mixed solution that step (1) obtains is heated with transpiring moisture in the water-bath of 100 DEG C, and constantly stir, obtain gelinite;
(3) dried in air dry oven by gelinite, bake out temperature is 150 DEG C, and drying time is 15 hours, obtains xerogel body;
(4) gelinite of drying is carried out pre-burning, calcined temperature is 600 DEG C, and burn-in time is 4 hours, obtains presoma; Presoma grinds after naturally cooling to room temperature, and calcined at 1000 DEG C by the presoma after grinding, calcination time is 20 hours, again grinds after naturally cooling to room temperature after calcining, namely obtains the positive electrode Li (Ni of doping vario-property
0.4co
0.2mn
0.4)
0.95cr
0.05o
1.95f
0.05.
(5) by the positive electrode of the above-mentioned doping vario-property prepared and the mass fraction clad material FePO than 4.0wt%
4be scattered in appropriate solvent, vigorous stirring at 80 DEG C, and regulate PH 9, until solvent volatilizees completely.Stirring terminates to leave standstill 1 hour and adopt quantitative filter paper to filter afterwards, and after spending deionized water 2 times under 80 DEG C of conditions dry 12 hours, namely last 450 DEG C of calcining 5h obtain end product Surface coating 4.0wt%FePO
4li (Ni
0.4co
0.2mn
0.4)
0.95cr
0.05o
1.95f
0.05.
Embodiment 5: the preparation method that a kind of lithium ion battery 442 type tertiary cathode is material modified, comprises the steps:
(1) analytically pure LiOHH is taken according to stoichiometric proportion (1.00:0.38:0.19:0.38:0.05:0.05)
2o, NiSO
46H
2o, CoSO
47H
2o, MnSO
4h
2o, C
16h
36o
4ti, LiF, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mixes rear concentrated ammonia liquor and pH value is adjusted to 7.5;
(2) mixed solution that step (1) obtains is heated with transpiring moisture in the water-bath of 90 DEG C, and constantly stir, obtain gelinite;
(3) dried in air dry oven by gelinite, bake out temperature is 120 DEG C, and drying time is 12 hours, obtains xerogel body;
(4) gelinite of drying is carried out pre-burning, calcined temperature is 500 DEG C, and burn-in time is 6 hours, obtains presoma; Presoma grinds after naturally cooling to room temperature, and calcined at 850 DEG C by the presoma after grinding, calcination time is 20 hours, again grinds after naturally cooling to room temperature after calcining, namely obtains the positive electrode Li (Ni of doping vario-property
0.4co
0.2mn
0.4)
0.95ti
0.05o
1.95f
0.05.
(5) by the above-mentioned doping vario-property positive electrode for preparing and the mass fraction clad material TiO than 2.0wt%
2be scattered in alcohol solvent, vigorous stirring at 80 DEG C, and regulate PH 9, until solvent volatilizees completely, stirring terminates to adopt quantitative filter paper to filter in latter standing 2 hours, and after spending deionized water 2 times under 82 DEG C of conditions dry 15 hours, namely last 480 DEG C of calcining 6h obtain end product Surface coating 2.0wt%TiO
2li (Ni
0.4co
0.2mn
0.4)
0.95ti
0.05o
1.95f
0.05.
Embodiment 6: the preparation method that a kind of lithium ion battery 442 type tertiary cathode is material modified, comprises the steps:
(1) analytically pure CH is taken according to stoichiometric proportion (1.00:0.388:0.194:0.388:0.03:0.05)
3cOOLi2H
2o, Ni (CH
3cOO)
24H
2o, Co (CH
3cOO)
24H
2o, Mn (CH
3cOO) 4H
2o, Al (NO
3)
29H
2o, LiCl, complete with deionized water dissolving respectively, add citric acid solution, the addition of citric acid solution equals the mole sum of transition metal ions, mixes rear concentrated ammonia liquor and pH value is adjusted to 7;
(2) mixed solution that step (1) obtains is heated with transpiring moisture in the water-bath of 80 DEG C, and constantly stir, obtain gelinite;
(3) dried in air dry oven by gelinite, bake out temperature is 100 DEG C, and drying time is 15 hours, obtains xerogel body;
(4) gelinite of drying is carried out pre-burning, calcined temperature is 600 DEG C, and burn-in time is 6 hours, obtains presoma; Presoma grinds after naturally cooling to room temperature, and calcined at 850 DEG C by the presoma after grinding, calcination time is 20 hours, again grinds after naturally cooling to room temperature after calcining, namely obtains the positive electrode Li (Ni of doping vario-property
0.4co
0.2mn
0.4)
0.97al
0.03o
1.95cl
0.05.
(5) by the positive electrode of the above-mentioned doping vario-property prepared and the mass fraction clad material TiO than 5.0wt%
2be scattered in water, vigorous stirring at 80 DEG C, and regulate PH to be 9, until solvent volatilizees completely, stirring terminates to adopt quantitative filter paper to filter in latter standing 2 hours, and after spending deionized water 2 times under 85 DEG C of conditions dry 18 hours, then namely 450 DEG C of calcining 5h obtain end product Surface coating 5.0wt%TiO
2li (Ni
0.4co
0.2mn
0.4)
0.97al
0.03o
1.95cl
0.05.
From in the X-ray diffracting spectrum of comparative example in Fig. 1 and embodiment 2,3,5, in embodiment 2,3,5, the positive electrode of synthesis has the hexagonal layer structure of high-sequential, there is not the impurity peaks belonging to doped chemical and clad material, the main peak (1003) of the XRD of each sample and (104) obviously sharp-pointed, and (101) and (006) peak divide significantly, illustrate that the positive electrode prepared in embodiment 2,3,5 in the present invention is obvious layer structure, crystal formation is good, and especially the layer structure of embodiment 5 is best.
From in the scanning electron microscope (SEM) photograph of comparative example in Fig. 2 and embodiment 2,3,5, more tiny and the even particle size distribution of comparative example particle, and smooth surface, degree of crystallinity is better, the embodiment after overdoping and coating modification, and material granule increases to some extent, particle agglomeration is tightr, in addition, the more significant change that modified material granule occurs is that material granule surface all attached to tiny particulate, and TiO is described
2, A1
2o
3with FePO
4clad material is all successfully coated on material granule surface.
By the positive electrode powder synthesized in embodiment 1-6, acetylene black, poly-inclined tetrafluoroethene (PVDF) mixes than 80:12:8 by mass fraction, uniform sizing material is ground to form after adding appropriate pyrrolidones, be spread evenly across on aluminium foil, dry at 100 DEG C, blunderbuss is cut (diameter 14mm), 3MPa rolls, make pole piece, use after 12 hours through 80 DEG C of vacuumizes, button (CR2032) test battery is assembled in the glove box being full of argon gas, negative electricity is lithium sheet very, electrolyte is LB315 [m (DMC): m (EMC): m (EC)=1:1:1] solution, barrier film is Celgard2325 hole film.The battery LAND-CT2001A assembled is carried out charge-discharge test.Discharge and recharge interval is 2.5-4.6V.
Because Li element in the positive electrode that obtains is volatile when high-temperature calcination, have the Li loss of about 5%, therefore the actual mole dosage of lithium salts comparatively theoretical amount want high by about 5%.
The battery that the positive electrode that comparative example and embodiment 2,3,5 are synthesized is assembled into is at normal temperature, and the Electrochemical Characterization result under 0.2C current density is as shown in table 1.
The battery that the positive electrode of comparative example and embodiment 2,3,5 is assembled, the first charge-discharge curve chart when normal temperature under 0.2C electric current is as shown in Figure 3; As shown in Figure 3, the battery charging and discharging curve of the positive electrode assembling prepared in the invention process 2,3,5 is very level and smooth, the voltage platform of charging curve is lower than the voltage platform of comparative example, and the discharge curve platform of embodiment 5 is higher than comparative example, best when also further illustrating embodiment 5, this result is consistent with XRD test result above.The battery that the positive electrode of comparative example and embodiment 2,3,5 is assembled, cyclic curve figure is at normal temperatures as shown in Figure 4, as shown in Figure 4, the circulating battery stability of the material of each embodiment is all than the height of comparative example, especially cyclical stability during embodiment 5 is best, comparative example and embodiment 2, 3, the battery that the positive electrode of 5 is assembled, when normal temperature respectively at 0.2C, 0.5C, 1C, 2.5C, under 0.2C multiplying power condition, the cyclic curve figure of each circulation 10 times as shown in Figure 5, as shown in Figure 5, adopt preparation method of the present invention, the volume positive electrode prepared in each embodiment is by coated, the chemical property of material is all improved, especially the effect that the TiO2 of 2% is coated is best.
Under table 10.2C current density, each embodiment charge-discharge performance test result is as shown in the table:
As shown in Table 1, compared with the positive electrode not having clad material with comparative example, in the present invention, in embodiment 1-embodiment 6, pass through TiO
2, A1
2o
3or FePO
4coated to positive electrode of clad material, the initial discharge specific capacity of the positive electrode prepared is improved, and cyclical stability is improved, the coated 2.0wt%TiO of especially preparation in embodiment 5
2li (Ni
0.4co
0.2mn
0.4)
0.95ti
0.05o
1.95f
0.05effect is best, and after 50 circulations, capability retention is 100%, and first discharge specific capacity is 187.8mAh/g.
Claims (10)
1. a lithium ion battery 442 type tertiary cathode is material modified, it is characterized in that: the positive electrode comprising doping vario-property, the outer layer covers of the positive electrode of described doping vario-property has one deck clad material, the quality of described clad material is the 1-5wt% of the positive electrode of doping vario-property, and the chemical general formula of the positive electrode of described doping vario-property is Li (Ni
0.4co
0.2mn
0.4)
1-xm
xo
2-yn
y, wherein, M is Ti, Mg, Al or Cr; N is F, Cl or Br, 0 < x≤0.10,0 < y≤0.10, and described clad material is TiO
2, A1
2o
3or FePO
4.
2. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 1 is material modified, is characterized in that: comprise the steps:
(1) water miscible lithium source, nickel source, manganese source, cobalt source, M salt, N salt and citric acid are dissolved in deionized water fully mix, then use ammoniacal liquor adjust ph to 7 ~ 8;
(2) the solution agitating heating at 60 ~ 100 DEG C step (1) obtained, obtains gelinite;
(3) by drying at step (2) gained gelinite 80 ~ 150 DEG C 8 ~ 15 hours, xerogel body is obtained;
(4) by xerogel body 300 ~ 600 DEG C of pre-calcination process 4 ~ 8 hours, naturally cool to grinding at room temperature and obtain presoma;
(5) presoma that step (4) obtains to be placed under 700 ~ 1000 DEG C of conditions roasting 10 ~ 20 hours, after cooling, to continue the positive electrode that grinding obtains doping vario-property;
(6) by the quality of clad material be doping vario-property positive electrode 1-5wt% weigh clad material, clad material is TiO
2, A1
2o
3or FePO
4;
(7) positive electrode of the above-mentioned doping vario-property prepared and clad material being scattered in the positive electrode making doping vario-property in water or ethanol and clad material dissolves completely, vigorous stirring at 40 ~ 80 DEG C, and regulate pH to 9 ~ 10, until solvent volatilizees completely, stirring terminates to adopt quantitative filter paper to filter in latter standing 1 ~ 2 hour, and after spending deionized water 1 ~ 2 time under 80 ~ 85 DEG C of conditions dry 12 ~ 20 hours, finally namely obtain end product at 400 ~ 500 DEG C of calcining 5 ~ 10h.
3. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 2 is material modified, it is characterized in that: described lithium source, nickel source, manganese source, cobalt source, M salt, N salt are (1-y) according to the mol ratio of lithium, nickel, manganese, cobalt, M, N: (0.4-x): (0.4-x): (0.2-x): x:y adds, wherein 0 < x≤0.10,0 < y≤0.10.
4. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 2 is material modified, is characterized in that: the integral molar quantity of described nickel salt, cobalt salt and manganese salt and the mol ratio of citric acid are 1:1 ~ 1:2.
5. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 2 is material modified, is characterized in that: described lithium source is LiNO
3, CH
3one or more in COOLi, LiOH.
6. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 2 is material modified, is characterized in that: described nickel source is Ni (NO
3)
2, Ni (CH
3cOO)
2, NiSO
4in one or more.
7. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 2 is material modified, is characterized in that: described manganese source is Mn (NO
3)
2, Mn (CH
3cOO)
2, MnSO
4in one or more.
8. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 2 is material modified, is characterized in that: described cobalt source is Co (NO
3)
2, Co (CH
3cOO)
2, CoSO
4in one or more.
9. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 2 is material modified, is characterized in that: described M salt is Mg (NO
3)
2, C
16h
36o
4ti, Al (NO
3)
3or Cr (NO
3)
3in one.
10. the preparation method that lithium ion battery 442 type tertiary cathode as claimed in claim 2 is material modified, is characterized in that: described N salt is the one in LiCl, LiF, LiBr.
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| CN106711414A (en) * | 2016-12-16 | 2017-05-24 | 江南大学 | 811-type ternary positive modified material for lithium ion batteries and preparation method thereof |
| CN107516730A (en) * | 2016-06-17 | 2017-12-26 | 珠海泰坦储能科技有限公司 | A kind of preparation of the lithium sulfur battery anode material of phosphoric acid iron and the lithium-sulfur cell containing this positive electrode |
| CN107910543A (en) * | 2017-12-13 | 2018-04-13 | 江南大学 | A kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof |
| CN109004197A (en) * | 2018-07-25 | 2018-12-14 | 广州大学 | A kind of preparation method of anode material for lithium-ion batteries |
| CN109417160A (en) * | 2016-07-04 | 2019-03-01 | Imec 非营利协会 | Ion is embedded in battery electrode and manufacturing method |
| WO2024041632A1 (en) * | 2022-08-26 | 2024-02-29 | 天津巴莫科技有限责任公司 | Ternary positive electrode material and preparation method therefor, positive electrode sheet, secondary battery, and electronic device |
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| CN104253273A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Anion/cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
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| CN104253273A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Anion/cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
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| CN107516730A (en) * | 2016-06-17 | 2017-12-26 | 珠海泰坦储能科技有限公司 | A kind of preparation of the lithium sulfur battery anode material of phosphoric acid iron and the lithium-sulfur cell containing this positive electrode |
| CN109417160A (en) * | 2016-07-04 | 2019-03-01 | Imec 非营利协会 | Ion is embedded in battery electrode and manufacturing method |
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| CN106711414A (en) * | 2016-12-16 | 2017-05-24 | 江南大学 | 811-type ternary positive modified material for lithium ion batteries and preparation method thereof |
| CN107910543A (en) * | 2017-12-13 | 2018-04-13 | 江南大学 | A kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof |
| CN109004197A (en) * | 2018-07-25 | 2018-12-14 | 广州大学 | A kind of preparation method of anode material for lithium-ion batteries |
| WO2024041632A1 (en) * | 2022-08-26 | 2024-02-29 | 天津巴莫科技有限责任公司 | Ternary positive electrode material and preparation method therefor, positive electrode sheet, secondary battery, and electronic device |
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