CN109411715A - A kind of high-performance lithium iron manganese phosphate anode material and preparation method thereof - Google Patents
A kind of high-performance lithium iron manganese phosphate anode material and preparation method thereof Download PDFInfo
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- CN109411715A CN109411715A CN201811076991.6A CN201811076991A CN109411715A CN 109411715 A CN109411715 A CN 109411715A CN 201811076991 A CN201811076991 A CN 201811076991A CN 109411715 A CN109411715 A CN 109411715A
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- H—ELECTRICITY
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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
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- H—ELECTRICITY
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- 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
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention discloses a kind of high-performance lithium iron manganese phosphate anode material and preparation method thereof.The strategy that the present invention is mutually cooperateed with using a kind of efficient ball-milling additive, compounded carbons with control precalcining, optimizes iron manganese phosphate for lithium (LiMnFe0.5Mn0.5PO4@C) positive electrode carbon-coating cladding, pore structure and promote its chemical property.After this method mixes lithium dihydrogen phosphate, ferrous oxalate, manganese carbonate and compounded carbons ball milling, utilize the fusing point of the compounded carbons feature different with thermal decomposition temperature, by the Effective Regulation of the precalcining temperature and time in synthesis process, uniform, the even particle size distribution and hierarchical porous structure " LiMnFe with carbon coating layer is prepared0.5Mn0.5PO4@C " positive electrode.The material has the characteristics that specific capacity is high, high rate performance is excellent and good cycling stability.Preparation process of the present invention is simple, convenient for expanding the scale of production.
Description
Technical field
The present invention relates to cell positive material fields, and in particular to a kind of to utilize efficient ball-milling additive, compounded carbons and control
The strategy preparation high-performance lithium iron manganese phosphate anode material that precalcining processed mutually cooperates with.
Background technique
Lithium ion battery olivine-type lithium iron manganese phosphate anode material is because its is cheap, environmental-friendly, cyclical stability
The advantages that good and good heat stability, the high-end fields such as power vehicle have been applied to it.However, lithium iron manganese phosphate anode material
The defects of electronic conductivity is low, lithium ion diffusion coefficient is small prevents its electro-chemical activity from being played well, hinders it
Further large-scale application.
For the electronic conductivity and lithium ion diffusion coefficient for improving iron manganese phosphate lithium material to improve its electrochemistry
Property, in recent years, researcher proposes various modified measures, mainly there is particle nanosizing, and carbon coating and progress metal are mixed
It is miscellaneous etc..Particle size is decreased to nanoscale, can effectively shorten the diffusion length of lithium ion, the ion for effectively improving material is led
Electric rate increases the reactivity of electrode material, but particle nanosizing be easy to cause material to reunite in cyclic process, and electrode adds
Work is difficult.Carbon coating can be effectively improved its conductivity, so that the chemical property of battery is improved, but it is homogeneous on the surface of the material
The technique of packet carbon is difficult to control, and different carbon sources can bring different results.In addition, the pattern of lithium iron manganese phosphate anode material
Feature also causes very big influence to its chemical property, and in general, porous character can make electrode material and electrolyte abundant
Contact, increases the reactivity of material, to improve its chemical property.Based on this, preparation has both various tactful advantage collaborations
The method for improving the chemical property of lithium iron manganese phosphate anode material has been the focus and emphasis problem of scientific research since consistent,
It is also the difficulties for promoting such material high performance.For example, Liu et al. prepares spherical structure with two step sol-gal processes
LiMn0.6Fe0.4PO4/ C-material, the material at 0.1C and 1 C charge and discharge current density, specific capacity respectively reach for
150 and 120 mAh/g(J. Alloy Compd,2014,587,133-137)；Wang etc. orients life on graphene film
Long LiMn0.75Fe0.25PO4Nanometer rods, the material of acquisition show excellent high rate performance, and the material is under the conditions of 20 C, ratio
Capacity is still up to 132 mAh/g(Angew Chem Int Ed,2011,50,7364-7368)；Oh etc. uses ultrasonic disperse
Pyrolysismethod synthesizes LiMn0.5Fe0.5PO4, simultaneously ball milling is then mixed with carbon source, obtains " LiMn0.5Fe0.5PO4@C " positive electrode, should
When material is with 0.5 and 2 C multiplying power discharging, first discharge specific capacity respectively reaches 150 and 121 mAh/g(J. Power Sources,2011,196,6924-6928).
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of utilization efficient ball-milling additive, composite carbon
Source and the carbon-coating cladding of the policy optimization lithium iron manganese phosphate anode material that mutually cooperates with of control precalcining, pore structure simultaneously promote its electrification
Learn performance.
A kind of policy optimization iron manganese phosphate for lithium mutually cooperateed with using efficient ball-milling additive, compounded carbons with control precalcining
(LiMnFe0.5Mn0.5PO4@C) positive electrode carbon-coating cladding, pore structure and the method for promoting its chemical property.Party's legal system
Standby material (LiFe0.5Mn0.5PO4@C, abbreviation LFMP C) it has the feature that with uniform carbon coating layer, classifying porous knot
Structure, large specific surface area and suitable partial size.Uniform carbon-coating improves the conductivity of material；Flourishing pore structure and larger compare table
The more diffusion admittances of area offer, guarantee electrolyte and active material come into full contact with；Suitable partial size can reduce lithium from
The diffusion length of son.The material specific capacity is high, high rate performance is excellent and stable cycle performance, and it is dynamic to be suitable for long-life high power type
The positive electrode of power lithium ion battery.
The above-mentioned policy optimization hole mutually cooperateed with using efficient ball-milling additive, compounded carbons and combination control precalcining is prepared to tie
Structure and the method for promoting lithium iron manganese phosphate anode material chemical property, include the following steps:
(1) by lithium dihydrogen phosphate, ferrous oxalate, manganese carbonate and appropriate compounded carbons ball milling mixing, wherein each element substance
The ratio between amount Li:Fe:Mn=2:1:1, using dehydrated alcohol, oleic acid and polyvinylpyrrolidone PVP mixed liquor as ball-milling additive, ball
Mill revolving speed is 400 rpm, and Ball-milling Time is 12 h, the suspension after obtaining ball milling；
(2) mixture obtained after filtering the suspension that step (1) obtains carries out 2 h of vacuum drying at 80 DEG C, before obtaining
Drive body dusty material；
(3) the precursor powder material that step (2) obtains is transferred to porcelain boat, under the protection of inert atmosphere, in certain temperature
Lower progress precalcining for a period of time, then is warming up to 650 DEG C and carries out 8 h(of calcining, and last cooled to room temperature obtains carbon coating
Lithium iron manganese phosphate anode material.
Further, the compounded carbons are the compound of sucrose and polyvinyl alcohol that mass ratio is 1:1.
Further, the quality of the compounded carbons and lithium dihydrogen phosphate, ferrous oxalate, manganese carbonate three gross mass
Ratio is 6:100.
Further, the dehydrated alcohol, tri- kinds of substances of oleic acid and polyvinylpyrrolidone PVP mass ratio be 60:
3:1。
Further, the precalcining, calcining heating rate be 5 DEG C/min, the temperature of precalcining is 350-
450 DEG C, burn-in time is 1-10 h.
A kind of high-performance lithium iron manganese phosphate anode material prepared by the above method, can be used for anode field.
Compared with prior art, the present invention has the advantage that
(1) preparation method of the present invention can mix carbon using dehydrated alcohol, oleic acid and PVP mixed liquor as ball-milling additive
Source, metal precursor and lithium dihydrogen phosphate effectively reduce the reunion between particle, improve grinding efficiency, advise convenient for expanding production
Mould；Meanwhile the feature different with thermal decomposition temperature using the fusing point of compounded carbons, can control carbon-coating the uniformity and original grain
The size of son and the pattern of particle buildup.
(2) LiFe of the method for the present invention preparation0.5Mn0.5PO4@C positive electrode material has relatively narrow particle diameter distribution, suitable grain
Diameter and graded porous structure, by being able to achieve carbon-coating and homogeneously coating and pore structure using compounded carbons and control burn-in time
Optimization, and then be effectively improved the chemical property of material.
(3) LiFe that the present invention is simply prepared0.5Mn0.5PO4@C positive electrode material shows high specific capacity, excellent follows
Ring and high rate performance.Wherein, the typical material (LiFe obtained in embodiment 40.5Mn0.5PO4@C) in 0.1,1,2 and 5 C multiplying powers
Lower progress charge/discharge test, specific discharge capacity respectively reach 155.3,130,122 and 108 mAh/g；It is recycled under 1 C multiplying power
After 100 circles, capacity retention ratio all reaches 95% or more.
Detailed description of the invention
Fig. 1 be in embodiment 1, embodiment 2 and embodiment 3 material LFMP-1, LFMP-2 and LFMP-3 for preparing at 25 DEG C
With the cycle performance figure under the conditions of 1 C multiplying power；
Fig. 2 be in embodiment 3, embodiment 4 and embodiment 5 material LFMP-3, LFMP-4 and LFMP-5 for preparing in 25 DEG C and 1 C
Cycle performance figure under the conditions of multiplying power；
Fig. 3 is material LFMP-4 and LFMP-6 the following under the conditions of 25 DEG C and 1 C multiplying power prepared in embodiment 4 and embodiment 6
Ring performance map；
Fig. 4 is the electron microscope of the material LFMP-4 prepared in embodiment 4, and wherein top half is the scanning electron microscope of material LFMP-4
(SEM) figure, lower half portion are transmission electron microscope (TEM) figure of material LFMP-4；
Fig. 5 is the high rate performance figure of the material LFMP-4 for preparing under the conditions of 25 DEG C and different multiplying in embodiment 4；
Fig. 6 be embodiment 1, embodiment 2, embodiment 3, embodiment 5 and embodiment 6 in prepare material LFMP-1, LFMP-2,
Transmission electron microscope (TEM) figure of LFMP-3, LFMP-5 and LFMP-6；
Fig. 7 be embodiment 1, embodiment 2, embodiment 3, embodiment 5 and embodiment 6 in prepare material LFMP-1, LFMP-2,
The high rate performance figure of LFMP-3, LFMP-5 and LFMP-6 under the conditions of 25 DEG C and different multiplying.
Specific embodiment
To show simply to control precalcining policy optimization pore structure in the present invention and promoting the carbon packet of chemical property
The superiority of lithium iron manganese phosphate anode material performance, present invention combination following specific embodiments and attached drawing are covered, this hair is discussed in detail
Bright content, but the embodiment of the present invention and protection scope are without being limited thereto.
Embodiment 1
(1) by LiH2PO4(2.0786 g), FeC2O4·2H2O(1.7989 g), MnCO3(1.1495 g) and sucrose (0.3678
G) it is placed in the zirconia ball grinding jar equipped with 30 g dehydrated alcohols, 1.5g oleic acid and 0.5 g PVP, with the revolving speed ball of 400 rpm
12 h are ground, suspension is obtained；
(2) mixture obtained after filtering the suspension that step (1) obtains is dried in vacuo, and dry 2 h are obtained at 80 DEG C
Precursor powder material；
(3) after the precursor powder material grinding obtained step (2), under being protected in argon atmosphere, with the liter of 5 DEG C/min
Warm speed rises to 400 DEG C, and 1 h is kept the temperature at 400 DEG C, is warming up to 650 DEG C later with the heating rate of 5 DEG C/min and keeps the temperature 8
H is cooled to room temperature, and obtains LFMP-1 positive electrode.
The cycle performance under 25 DEG C and 1 C multiplying power of material LFMP-1 obtained is as shown in Figure 1.As shown in Figure 1,
For LFMP-1 positive electrode under 25 DEG C and 1 C multiplying power, first circle specific discharge capacity is 117.3 mAh/g, 100 circle of circulation, capacity guarantor
Holdup is 89 %.
The microscopic appearance of material LFMP-1 obtained is as shown in Figure 6.It will be appreciated from fig. 6 that LFMP-1 material granule is reunited more
Seriously.
High rate performance figure of the material LFMP-1 obtained under the conditions of 25 DEG C and different multiplying is as shown in Figure 7.It can by Fig. 7
Know, specific discharge capacity of the LFMP-1 positive electrode under 25 DEG C and 0.1 C, 1 C and 5 C multiplying powers is respectively 140.6,116.7 Hes
96.3 mAh/g。
Embodiment 2
(1) by LiH2PO4(2.0786 g), FeC2O4·2H2O(1.7989 g), MnCO3(1.1495 g) and polyvinyl alcohol
(0.3678 g) is placed in the zirconia ball grinding jar equipped with 30 g dehydrated alcohols, 1.5g oleic acid and 0.5 g PVP, with 400 rpm
12 h of revolving speed ball milling, obtain suspension；
(2) mixture obtained after filtering the suspension that step (1) obtains is dried in vacuo, and dry 2 h are obtained at 80 DEG C
Precursor powder material；
(3) after the precursor powder material grinding obtained step (2), under being protected in argon atmosphere, with the liter of 5 DEG C/min
Warm speed rises to 400 DEG C, and 1 h is kept the temperature at 400 DEG C, is warming up to 650 DEG C later with the heating rate of 5 DEG C/min and keeps the temperature 8
H is cooled to room temperature, and obtains LFMP-2 positive electrode.
The cycle performance under 25 DEG C and 1 C multiplying power of material LFMP-2 obtained is as shown in Figure 1.As shown in Figure 1,
For LFMP-2 positive electrode under 25 DEG C and 1 C multiplying power, first circle specific discharge capacity is 123.3 mAh/g, 100 circle of circulation, capacity guarantor
Holdup is 93 %.
The microscopic appearance of material LFMP-2 obtained is as shown in Figure 6.It will be appreciated from fig. 6 that LFMP-2 material granule is reunited more
Seriously.
High rate performance figure of the material LFMP-2 obtained under the conditions of 25 DEG C and different multiplying is as shown in Figure 7.It can by Fig. 7
Know, specific discharge capacity of the LFMP-2 positive electrode under 25 DEG C and 0.1 C, 1 C and 5 C multiplying powers is respectively 146.5,121.5 Hes
101.1 mAh/g。
Embodiment 3
(1) by LiH2PO4(2.0786 g), FeC2O4·2H2O(1.7989 g), MnCO3(1.1495 g) and compounded carbons
(0.3678 g) is placed in the zirconia ball grinding jar equipped with 30 g dehydrated alcohols, 1.5g oleic acid and 0.5 g PVP, with 400 rpm
12 h of revolving speed ball milling, obtain suspension；
(2) mixture obtained after filtering the suspension that step (1) obtains is dried in vacuo, and dry 2 h are obtained at 80 DEG C
Precursor powder material；
(3) after the precursor powder material grinding obtained step (2), under being protected in argon atmosphere, with the liter of 5 DEG C/min
Warm speed rises to 400 DEG C, and 1 h is kept the temperature at 400 DEG C, is warming up to 650 DEG C later with the heating rate of 5 DEG C/min and keeps the temperature 8
H is cooled to room temperature, and obtains LFMP-3 positive electrode.
The cycle performance under 25 DEG C and 1 C multiplying power of material LFMP-3 obtained is as shown in Figure 1.As seen from Figure 1, Figure 2,
For LFMP-3 positive electrode under 25 DEG C and 1 C multiplying power, first circle specific discharge capacity is 129.7 mAh/g, 100 circle of circulation, capacity guarantor
Holdup is 94 %.
The microscopic appearance of material LFMP-3 obtained is as shown in Figure 6.It will be appreciated from fig. 6 that LFMP-3 material granule is reunited more
Seriously.
High rate performance figure of the material LFMP-3 obtained under the conditions of 25 DEG C and different multiplying is as shown in Figure 7.It can by Fig. 7
Know, specific discharge capacity of the LFMP-3 positive electrode under 25 DEG C and 0.1 C, 1 C and 5 C multiplying powers is respectively 1150.4,125.3
With 98.7 mAh/g.
Embodiment 4
(1) by LiH2PO4(2.0786 g), FeC2O4·2H2O(1.7989 g), MnCO3(1.1495 g) and compounded carbons
(0.3678 g) is placed in the zirconia ball grinding jar equipped with 30 g dehydrated alcohols, 1.5g oleic acid and 0.5 g PVP, with 400 rpm
12 h of revolving speed ball milling, obtain suspension；
(2) mixture obtained after filtering the suspension that step (1) obtains is dried in vacuo, and dry 2 h are obtained at 80 DEG C
Precursor powder material；
(3) after the precursor powder material grinding obtained step (2), under being protected in argon atmosphere, with the liter of 5 DEG C/min
Warm speed rises to 400 DEG C, and 5 h are kept the temperature at 400 DEG C, is warming up to 650 DEG C later with the heating rate of 5 DEG C/min and keeps the temperature 8
H is cooled to room temperature, and obtains LFMP-4 positive electrode.
Cycle performance of the material LFMP-4 obtained under 25 DEG C and 1 C multiplying power is as shown in Figure 2.By Fig. 2, Fig. 3 it is found that
For LFMP-4 positive electrode under 25 DEG C and 1 C multiplying power, first circle specific discharge capacity is 130.1 mAh/g, 100 circle of circulation, capacity guarantor
Holdup is 98.5 %.
The microscopic appearance of material LFMP-4 obtained is as shown in Figure 4.As shown in Figure 4, LFMP-4 material particle size is smaller,
Even particle size distribution and have uniform carbon coating layer.
High rate performance figure of the material LFMP-4 obtained under the conditions of 25 DEG C and different multiplying is as shown in Figure 5.It can by Fig. 5
Know, specific discharge capacity of the LFMP-4 positive electrode under 25 DEG C and 0.1 C, 1 C and 5 C multiplying powers is respectively 155.0,141.5 Hes
119.5 mAh/g。
Embodiment 5
(1) by LiH2PO4(2.0786 g), FeC2O4·2H2O(1.7989 g), MnCO3(1.1495 g) and compounded carbons
(0.3678 g) is placed in the zirconia ball grinding jar equipped with 30 g dehydrated alcohols, 1.5g oleic acid and 0.5 g PVP, with 400 rpm
12 h of revolving speed ball milling, obtain suspension；
(2) mixture obtained after filtering the suspension that step (1) obtains is dried in vacuo, and dry 2 h are obtained at 80 DEG C
Precursor powder material；
(3) after the precursor powder material grinding obtained step (2), under being protected in argon atmosphere, with the liter of 5 DEG C/min
Warm speed rises to 400 DEG C, and 10 h are kept the temperature at 400 DEG C, is warming up to 650 DEG C later with the heating rate of 5 DEG C/min and keeps the temperature
8 h, are cooled to room temperature, and obtain LFMP-5 positive electrode.The cyclicity under 25 DEG C and 1 C multiplying power of material LFMP-5 obtained
It can be as shown in Figure 2.As shown in Figure 2, for LFMP-5 positive electrode under 25 DEG C and 1 C multiplying power, first circle specific discharge capacity is 129.2
MAh/g, 100 circle of circulation, capacity retention ratio is 90 %.
The microscopic appearance of material LFMP-5 obtained is as shown in Figure 6.It will be appreciated from fig. 6 that LFMP-5 material granule is reunited more
Seriously.
High rate performance figure of the material LFMP-5 obtained under the conditions of 25 DEG C and different multiplying is as shown in Figure 7.It can by Fig. 7
Know, specific discharge capacity of the LFMP-5 positive electrode under 25 DEG C and 0.1 C, 1 C and 5 C multiplying powers is respectively 144.6,128.9 Hes
100.6 mAh/g。
Embodiment 6
(1) by LiH2PO4(2.0786 g), FeC2O4·2H2O(1.7989 g), MnCO3(1.1495 g) and compounded carbons
(0.3678 g) is placed in the zirconia ball grinding jar equipped with 30 g dehydrated alcohols, 1.5g oleic acid and 0.5 g PVP, with 400 rpm
12 h of revolving speed ball milling, obtain suspension；
(2) mixture obtained after filtering the suspension that step (1) obtains is dried in vacuo, and dry 2 h are obtained at 80 DEG C
Precursor powder material；
(3) after the precursor powder material grinding obtained step (2), under being protected in argon atmosphere, with the liter of 5 DEG C/min
Warm speed rises to 350 DEG C, and 5 h are kept the temperature at 350 DEG C, is warming up to 650 DEG C later with the heating rate of 5 DEG C/min and keeps the temperature 8
H is cooled to room temperature, and obtains LFMP-6 positive electrode.
The cycle performance under 25 DEG C and 1 C multiplying power of material LFMP-6 obtained is as shown in Figure 3.From the figure 3, it may be seen that
For LFMP-6 positive electrode under 25 DEG C and 1 C multiplying power, first circle specific discharge capacity is 125.2 mAh/g, 100 circle of circulation, capacity guarantor
Holdup is 90 %.
The microscopic appearance of material LFMP-6 obtained is as shown in Figure 6.It will be appreciated from fig. 6 that LFMP-6 material granule is reunited more
Seriously.
High rate performance figure of the material LFMP-6 obtained under the conditions of 25 DEG C and different multiplying is as shown in Figure 7.It can by Fig. 7
Know, specific discharge capacity of the LFMP-6 positive electrode under 25 DEG C and 0.1 C, 1 C and 5 C multiplying powers is respectively 140.5,119.8 Hes
94.0 mAh/g。
Claims (6)
1. a kind of preparation method of high-performance lithium iron manganese phosphate anode material, which comprises the steps of:
(1) by lithium dihydrogen phosphate, ferrous oxalate, manganese carbonate and compounded carbons ball milling mixing, wherein the amount of each element substance it
Than for Li:Fe:Mn=2:1:1, using dehydrated alcohol, oleic acid and polyvinylpyrrolidone PVP mixed liquor as ball-milling additive, ball milling
Revolving speed is 400 rpm, and Ball-milling Time is 12 h, the suspension after obtaining ball milling；
(2) mixture obtained after filtering the suspension that step (1) obtains carries out 2 h of vacuum drying at 80 DEG C, before obtaining
Drive body dusty material；
(3) the precursor powder material that step (2) obtains is transferred to porcelain boat, under the protection of inert atmosphere, carries out precalcining,
It is warming up to 650 DEG C again and carries out 8 h of calcining, last cooled to room temperature obtains carbon coating lithium iron manganese phosphate anode material.
2. preparation method according to claim 1, it is characterised in that in step (1), the compounded carbons are that mass ratio is
The sucrose of 1:1 and the compound of polyvinyl alcohol.
3. preparation method according to claim 1, it is characterised in that in step (1), the quality and phosphorus of the compounded carbons
Acid dihydride lithium, ferrous oxalate, manganese carbonate three gross mass ratio be 6:100.
4. preparation method according to claim 1, it is characterised in that in the step (1), the dehydrated alcohol, oleic acid and
The mass ratio of tri- kinds of substances of polyvinylpyrrolidone PVP is 60:3:1.
5. preparation method according to claim 1, it is characterised in that in step (3), the precalcining, the heating of calcining are fast
Rate is 5 DEG C/min, and the temperature of precalcining is 350-450 DEG C, and burn-in time is 1-10 h.
6. a kind of high-performance lithium iron manganese phosphate anode material as made from any one of the claim 1-5 preparation method.
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| CN112054261A (en) * | 2020-07-28 | 2020-12-08 | 昆明理工大学 | Method for recovering waste lithium battery positive electrode through mechanical activation assisted spray pyrolysis |
| CN112151804A (en) * | 2020-09-27 | 2020-12-29 | 广州大学 | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof |
| CN113161523A (en) * | 2021-03-31 | 2021-07-23 | 华南理工大学 | Non-stoichiometric lithium manganese iron phosphate cathode material and preparation method and application thereof |
| CN114975985A (en) * | 2022-06-29 | 2022-08-30 | 三明市新能源产业技术研究院有限公司 | Ti-Cr co-doped high-voltage spinel cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN115050934A (en) * | 2022-05-31 | 2022-09-13 | 四川大学 | Hydrophobic oleophilic Na 2 Fe 2 （SO 4 ） 3 /C positive electrode material and preparation method thereof |
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