CN107146877B - Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery - Google Patents

Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery Download PDF

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CN107146877B
CN107146877B CN201710304314.4A CN201710304314A CN107146877B CN 107146877 B CN107146877 B CN 107146877B CN 201710304314 A CN201710304314 A CN 201710304314A CN 107146877 B CN107146877 B CN 107146877B
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CN107146877A (en
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邵刚勤
范书豪
毛家威
马霏霏
朱璨
张安乐
谢贵振
晏佳礼
顾佳妮
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Wuhan University of Technology WUT
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    • HELECTRICITY
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    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
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    • H01M4/58Selection 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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Abstract

The invention belongs to the technical field of electrochemical energy storage new materials and preparation thereof. The invention provides a preparation method of a fluoxaphosphate lithium ion battery material, a positive plate and a lithium ion battery. The method comprises the following steps: 1) LiFe1‑xVxPO4F1‑δOδ(x ═ 0, 0.1, 0.3, 0.5, 0.7, and 1, δ ≦ 0.4) preparation of powder: according to LiFe1‑xVxPO4F1‑δOδWeighing iron phosphate, vanadium phosphate and lithium source powder according to a metering ratio, grinding, and calcining in inert gas to obtain LiFe1‑xVxPO4F1‑δOδA pure phase powder. LiFe1‑ xVxPO4F1‑δOδPreparing a positive plate: mixing LiFe1‑ xVxPO4F1‑δOδBall milling the pure phase powder and the nano conductive carbon to obtain LiFe1‑xVxPO4F1‑δOδCoating the powder with C, mixing LiFe1‑ xVxPO4F1‑δOδMixing the/C powder and the adhesive according to the mass ratio, dissolving in an organic solvent, coating on an aluminum foil after stirring, and drying to obtain the LiFe1‑xVxPO4F1‑δOδAnd (4) a positive plate. The battery material prepared by the invention has good cycle performance at 0.1C rate.

Description

Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery
Technical Field
The invention relates to a fluoroxyphosphate (LiFe)1-xVxPO4F1-δOδ) A preparation method of a lithium ion battery material, a positive plate and a lithium ion battery belong to the technical field of novel electrochemical energy storage materials and preparation thereof.
Background
3.45V lithium iron phosphate (LiFePO) having an olivine structure4) Compared with a lithium ion battery, the lithium iron fluorophosphate (LiFePO) with the Tavorite structure4F) The ionic conductivity of the metal oxide is improved by more than two orders of magnitude, but unfortunately, the working voltage is lower and is only 2.8V, and other high-reduction oxidation couple such as V in a non-fluorine system is used for reference to solve the problem3+/V4+(4.2V) etc. in place of Fe2+/V3+An electric pairing method (B.Yang, et al., J.Phys.chem.Solids,87:228,2015; P.F.Xiao, et al., Solid State Ionics,242:10,2013; J.Barker, et al., electrochem.Solid-State Lett.,8: A285,2005; J.Barker, et al., Eur.Phys.J.Appl.Phys.,35:47749,2004) to improve the technical idea of the fluorine-containing system voltage platform.
Lithium iron fluorophosphate (LiFePO)4F) Lithium vanadium fluorophosphate (LiVPO)4F) Lithium vanadyl phosphate (LiVPO)4O) and solid solutions thereof, most of which relate to the synthesis of a single material, without the presence of a fluorooxyphosphate(LiFe1- xVxPO4F1-δOδ) And (5) related reports.
Disclosure of Invention
Aiming at the defects of the existing battery material, the invention aims to provide a preparation method of a fluoxaphosphate lithium ion battery material, a positive plate and a lithium ion battery.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
fluorooxyphosphate lithium ion battery material LiFe1-xVxPO4F1-δOδThe preparation method of (1), wherein x is 0-1 and δ is not more than 0.4; the method comprises the following steps:
1) according to VPO4Weighing the following components in a metering ratio: grinding and mixing vanadium source and phosphorus source raw materials, calcining for 3-8 hours in inert gas at 200-400 ℃, and cooling to room temperature to obtain powder;
2) grinding and mixing the powder obtained in the step 1) for 0.5-2 hours, calcining the mixture in inert gas at 700-900 ℃ for 4-10 hours, and cooling the mixture to room temperature to obtain VPO4A powder as a main phase;
3)LiFe1-xVxPO4F1-δOδpreparation of powder: according to LiFe1-xVxPO4F1-δOδWeighing ferric phosphate, lithium fluoride powder and the vanadium phosphate prepared in the step 2) according to a metering ratio, and grinding to obtain Li-Fe-V-P-O-F precursor powder, wherein the molar weight of the lithium fluoride powder is 1-1.05 times of the total molar weight of the ferric phosphate and the vanadium phosphate powder;
4) calcining Li-Fe-V-P-O-F precursor powder in inert gas at the temperature of 575-675 ℃ for 1.5-6 hours, and grinding to obtain LiFe1-xVxPO4F1-δOδA pure phase powder.
In the scheme, in the step 1): the vanadium source is one of vanadium trioxide or vanadium pentoxide.
In the scheme, in the step 1): the phosphorus source is one of diammonium hydrogen phosphate or phosphorous acid.
In the above scheme, x is 0.1, 0.3, 0.5, 0.7 or 1.
In the above scheme, the inert gas is argon or nitrogen.
A preparation method of a fluorine oxygen phosphate lithium ion battery positive plate comprises the following steps:
1) mixing the LiFe1-xVxPO4F1-δOδMixing the pure-phase powder and the nano conductive carbon according to the mass ratio of 3: 1-8: 1, and performing ball milling to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder;
2) mixing LiFe1-xVxPO4F1-δOδMixing the/C powder and polyvinylidene fluoride according to a mass ratio of 9: 1-9.5: 0.5, dissolving in N-methyl pyrrolidone, stirring until the viscosity is 3000-6000 mPa.s, coating on an aluminum foil, and drying in vacuum to obtain LiFe1- xVxPO4F1-δOδAnd (4) a positive plate.
In the scheme, in the step 1): the nano conductive carbon is a carbon particle, a carbon nanotube or a graphene carbon source with a size of less than 100nm in at least one direction.
In the scheme, in the step 1): the ball milling time is 4-8 hours.
In the scheme, in the step 2): LiFe1-xVxPO4F1-δOδThe mass ratio of the/C powder to the N-methyl pyrrolidone is 1: 7-1: 9.
A lithium ion battery comprising a positive electrode sheet as described above.
The invention also provides an assembly of the oxyfluoride phosphate lithium ion battery, which comprises the following steps:
1) mixing LiFe1-xVxPO4F1-δOδAssembling the positive plate, the lithium negative plate, the diaphragm, the electrolyte and the battery case fitting in a glove box with oxygen content and water content lower than 1 ppm;
2) and standing for 10-16 hours after the lithium ion battery is assembled, and carrying out related electrochemical performance tests.
The solute of the electrolyte is one of lithium hexafluorophosphate and lithium dioxalate borate; the solvent of the electrolyte is one or a mixture of several of ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate according to any proportion; the concentration of the electrolyte is 1-1.2 mol/L. The diaphragm is one of a polypropylene diaphragm and a glass fiber diaphragm.
LiFe obtained by the invention1-xVxPO4F1-δOδ(x is 0, 0.1, 0.3, 0.5, 0.7 and 1, delta is not more than 0.4) the first discharge capacity of the lithium ion battery is 150.3 mA.h.g at 20 ℃ (0.1C multiplying power)-1(x=0)、148.4mA·h·g-1(x=0.1)、152.3mA·h·g-1(x=0.3)、191.9mA·h·g-1(x=0.5)、192.6mA·h·g-1(x ═ 0.7) and 191.1mA · h · g-1(x ═ 1), and the discharge capacities were 148.2mA · h · g, respectively, after 30 cycles-1、142.5mA·h·g-1、105mA·h·g-1、10mA·h·g-1、30mA·h·g-1And 1.9 mA. h. g-1The capacity retention rates were 98.8%, 95.20%, 68.94%, 6.03%, 17.78%, and 0.99%, respectively.
The invention has the beneficial effects that:
1. the high capacity of the battery material can be effectively ensured by adopting a nano carbon coating method;
2. synthesize pure phase LiFe1-xVxPO4F1-δOδTraces of (A) are only found possible under very harsh detection conditions<2 wt.%) heterophasic phase;
3. the oxyfluoride phosphate lithium ion battery has very high discharge capacity and capacity retention rate (x is more than or equal to 0 and less than or equal to 0.3, and the stability is good) under the multiplying power of 0.1C.
The invention can be popularized to other fluorophosphate lithium ion battery materials and preparation methods thereof, such as XaMb(PO4)cFdO1-d(X ═ Li, Na or mixtures thereof; M ═ Fe, V, Mn, Ni, Co, Cu, Ti, Al, Cr, Mo, Nb or mixtures thereof; 0<a≤5,0<b≤3,0<c is less than or equal to 3, d is 0.1-1) and the like, and a preparation method thereof.
Drawings
FIG. 1 is a LiFe prepared in example one1-xVxPO4F1-δOδX-ray diffraction (XRD) pattern of the powder.
Fig. 2 is a charge-discharge cycle curve of the fluorophosphate lithium ion battery prepared in the first embodiment under 20 ℃ (0.1C rate).
Fig. 3 is a charge-discharge cycle curve of the lithium ion battery of the fluorophosphates prepared in example four under 20 ℃ (0.1C rate).
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
The first embodiment is as follows:
a preparation method of a fluoxaphosphate lithium ion battery material comprises the following steps:
s1.1 according to VPO4Weighing V in metering ratio2O5And H3PO3Grinding and mixing the raw materials, sieving the raw materials by using a 120-mesh sieve, and batching the raw materials to obtain V-P-O mixed powder. And presintering the mixed powder in argon at 300 ℃ for 6 hours, and cooling to room temperature to obtain powder. Grinding the powder for 0.5 hour, calcining at 870 deg.C for 8 hours in argon gas, cooling to room temperature to obtain VPO4Powder of the main phase.
S1.2 according to LiFe1-xVxPO4F1-δOδWeighing commercially available ferric phosphate, vanadium phosphate prepared from S1.1 and lithium fluoride powder (the molar amount of the lithium fluoride powder is 1.05 times of the total molar amount of the ferric phosphate and the vanadium phosphate powder) according to the metering ratio (x is 0, 0.1, 0.3, 0.5, 0.7 and 1, and delta is less than or equal to 0.4), and grinding to obtain Li-Fe-V-P-O-F precursor powder;
s1.3 calcining Li-Fe-V-P-O-F precursor powder in argon at 625 ℃ for 4.5 hours, and grinding for 1 hour to obtain LiFe1-xVxPO4F1-δOδA pure phase powder.
S1.4 reaction of LiFe1-xVxPO4F1-δOδMixing the pure phase powder and the nano conductive carbon according to the mass ratio of 7:2, and performing ball milling for 8 hours to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder.
S1.5 reacting LiFe1-xVxPO4F1-δOδMixing the/C powder with a polyvinylidene fluoride adhesive in a mass ratio of 9:1, dissolving in N-methyl pyrrolidone, and obtaining LiFe1-xVxPO4F1-δOδThe mass ratio of the/C powder to the N-methyl pyrrolidone is 1:7, the mixture is coated on an aluminum foil when the mixture is stirred until the viscosity is 3000mPa & s, and the mixture is dried in vacuum to obtain LiFe1-xVxPO4F1-δOδA positive plate;
S1.6LiPF6EC/DMC electrolyte: the concentration of the electrolyte is 1mol/L, and the solute is LiPF6The solvent was EC/DMC (1:1, vol.%).
S1.7 reacting LiFe1-xVxPO4F1-δOδAssembling the positive plate, the lithium negative plate, the polypropylene diaphragm, the electrolyte and the battery shell fitting in a glove box with oxygen content and water content lower than 1ppm, wherein the concentration of the electrolyte is 1mol/L, and the solute is LiPF6The solvent was EC/DMC (1:1, vol.%). After the assembly, the mixture was allowed to stand for 10 hours and subjected to a charge-discharge cycle at 20 ℃ (0.1C magnification).
FIG. 1 is a LiFe prepared in example one1-xVxPO4F1-δOδX-ray diffraction (XRD) pattern of the powder, the results show that: the invention synthesizes a series of LiFe1-xVxPO4F1-δOδPure phase powder of LiFe1-xVxPO4F1-δOδThe pure phase powders are respectively marked LFPF (LiFePO)4F)、LF0.9V0.1PF1-δOδ(LFe0.9V0.1PO4F1-δOδ)、LF0.7V0.3PF1-δOδ(LFe0.7V0.3PO4F1-δOδ)、LF0.5V0.5PF1-δOδ(LFe0.5V0.5PO4F1-δOδ)、LF0.3V0.7PF1-δOδ(LFe0.3V0.7PO4F1-δOδ)、LVPF1-δOδ(LVPO4F1-δOδ)。
Fig. 2 is a charge-discharge cycle curve of the lithium-ion oxyfluoride phosphate battery prepared in the first example at 20 ℃ (0.1C rate). It can be seen that the discharge plateaus of the batteries are about 2.8V and 4.2V, and the first discharge capacities are 150.3 mA.h.g-1(x=0)、148.4mA·h·g-1(x=0.1)、152.3mA·h·g-1(x=0.3)、191.9mA·h·g-1(x=0.5)、192.6mA·h·g-1(x ═ 0.7) and 191.1mA · h · g-1(x ═ 1), the capacity gradually increased with increasing vanadium content. When the discharge capacity is circulated for 30 times, the discharge capacity is respectively 148.2 mA.h.g-1、142.5mA·h·g-1、105mA·h·g-1、10mA·h·g-1、30mA·h·g-1And 1.9 mA. h. g-1The capacity retention rates are respectively 98.8%, 95.20%, 68.94%, 6.03%, 17.78% and 0.99%, LiFe1-xVxPO4F1-δOδ(x is more than or equal to 0 and less than or equal to 0.3), good cycle stability and LiFe1-xVxPO4F1-δOδAmong the series batteries, LFe0.9V0.1PO4F1-δOδThe comprehensive performance is best, the first discharge capacity and the cycle performance are excellent, and the LiFePO has two discharge voltage platforms of 2.8V and 4.2V4The performance of the F battery is excellent, but the battery has a discharge voltage platform of only 2.8V and has lower voltage.
Example two:
the second example was the same as the first example except that the V-P-O mixed powder was changed in the raw material, calcination temperature and time.
S1.1 according to VPO4Weighing V in metering ratio2O3And NH4H2PO4Grinding and mixing the raw materials, sieving the raw materials by using a 120-mesh sieve, and batching the raw materials to obtain V-P-O mixed powder. Presintering the mixed powder in argon gas at 200 ℃ for 8 hours to obtain powderGrinding for 2 hours, calcining in argon at 700 ℃ for 10 hours to obtain VPO4Powder as the main phase, LiFe was obtained according to the procedure of example one1-xVxPO4F1-δOδThe discharge capacities of the batteries were 126.5mA · h · g, respectively, when the batteries were cycled up to 30 times-1(x=0)、81.9mA·h·g-1(x=0.1)、0.6mA·h·g-1(x=0.3)、6.3mA·h·g-1(x=0.5)、22.7mA·h·g-1(x ═ 0.7) and 5.4mA · h · g-1(x ═ 1), the capacity retention rate was 94.21%, 71.35%, 2.13%, 3.12%, 9.28%, and 2.35%.
Example three:
the calcination temperature and time of the V-P-O mixed powder in example III were the same as those in example I except that they were changed.
S1.1 preparing V-P-O mixed powder according to example II, presintering the mixed powder in argon gas at 400 ℃ for 3 hours, grinding the obtained powder for 2 hours, and calcining the powder in argon gas at 900 ℃ for 4 hours to obtain VPO4Powder as the main phase, LiFe was obtained according to the procedure of example one1-xVxPO4F1-δOδThe discharge capacities of the batteries were 125.8mA · h · g, respectively, when the batteries were cycled for 30 times-1(x=0)、75.6mA·h·g-1(x=0.1)、1.5mA·h·g-1(x=0.3)、7.2mA·h·g-1(x=0.5)、23.5mA·h·g-1(x ═ 0.7) and 6.2mA · h · g-1(x ═ 1), the capacity retention was 95.71%, 74.52%, 3.26%, 4.27%, 9.12%, and 2.17%.
Comparative example one:
the comparative example was identical to example one, except that the preparation method of the V-P-O mixed powder (carbothermic method) was different.
S1.1 according to VPO4Weighing V in metering ratio2O5、NH4H2PO4And carbon powder (25% excess), milling, mixing, and calcining at 750 ℃ for 4 hours in argon to obtain VPO4The target product was obtained according to the procedure of example one, and XRD results of the target product showed that LiFe was not synthesized1-xVxPO4F1-δOδPowder and more impurity phases, which are fully explained in the preparation of LiFe1- xVxPO4F1-δOδIn the process of preparing the powder, VPO is prepared by adopting a carbothermic method4The powder, in which carbon powder is mixed, may reduce ferric ions to ferrous ions in minute amounts, further resulting in experimental failure.
Example four:
example four was the same as example one, except that the calcination temperature and time of the Li-Fe-V-P-O-F precursor powder were different.
S1.1 preparing Li-Fe-V-P-O-F precursor powder according to the first embodiment, calcining the Li-Fe-V-P-O-F precursor powder in argon at 625 ℃ for 1.5 hours, and grinding to obtain LiFe1-xVxPO4F1-δOδA pure phase powder.
FIG. 3 is a charge-discharge cycle curve of the lithium ion battery of oxyfluoride phosphate obtained in example four at 20 deg.C (0.1C rate), and it can be seen that the discharge capacities were 125.3mA h g respectively at 30 cycles-1(x=0)、84.4mA·h·g-1(x=0.1)、0.1mA·h·g-1(x=0.3)、32.7mA·h·g-1(x=0.5)、31.5mA·h·g-1(x ═ 0.7) and 64.9mA · h · g-1(x ═ 1), the capacity retention ratio was 92.19%, 80.84%, 0.11%, 21.21%, 25.09%, and 38.44%.
Example five:
example five is the same as example one, except that the calcination temperature and time of the Li-Fe-V-P-O-F precursor powder were different.
S1.1 calcining Li-Fe-V-P-O-F precursor powder in argon at 575 ℃ for 6 hours, and grinding to obtain LiFe1- xVxPO4F1-δOδA pure phase powder. Thus obtaining LiFe1-xVxPO4F1-δOδThe discharge capacities of the batteries were 116.5mA · h · g, respectively, when the batteries were cycled up to 30 times-1(x=0)、82.3mA·h·g-1(x=0.1)、0.5mA·h·g-1(x=0.3)、4.2mA·h·g-1(x=0.5)、21.2mA·h·g-1(x ═ 0.7) and 4.5mA · h · g-1(x ═ 1), the capacity retention ratio was 93.12%, 70.35%, 0.13%, 2.52%, 10.98%, and 2.47%.
Example six:
example six is the same as example one, except that the calcination temperature and time of the Li-Fe-V-P-O-F precursor powder were varied.
S1.1 calcining Li-Fe-V-P-O-F precursor powder for 1.5 hours in argon at 675 ℃, and grinding to obtain LiFe1- xVxPO4F1-δOδA pure phase powder. Thus obtaining LiFe1-xVxPO4F1-δOδThe discharge capacities of the batteries were 113.2mA · h · g, respectively, when the batteries were cycled up to 30 times-1(x=0)、81.9mA·h·g-1(x=0.1)、0.4mA·h·g-1(x=0.3)、3.6mA·h·g-1(x=0.5)、22.3mA·h·g-1(x ═ 0.7) and 4.3mA · h · g-1(x ═ 1), the capacity retention ratio was 94.27%, 71.27%, 0.15%, 2.56%, 10.87%, and 2.61%.
Example seven:
example seven is the same as example one, except that the proportions of the conductive agent, the binder and the solvent are different.
S1.1 Life from example one1-xVxPO4F1-δOδMixing the pure phase powder and the nano conductive carbon according to the mass ratio of 8:1, and performing ball milling for 4 hours to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder.
S1.2 reacting LiFe1-xVxPO4F1-δOδMixing the/C powder with polyvinylidene fluoride adhesive in a mass ratio of 9.5:0.5, dissolving in N-methyl pyrrolidone, and obtaining LiFe1-xVxPO4F1-δOδThe mass ratio of the/C powder to the N-methyl pyrrolidone is 1:9, the mixture is stirred until the viscosity is 6000 mPa.s, the mixture is coated on an aluminum foil, and the mixture is dried in vacuum to obtain LiFe1-xVxPO4F1-δOδA positive plate; LiFe thus obtained1-xVxPO4F1-δOδWhen the battery is cycled for 30 times, the discharge capacity is respectively 112.7 mA.h.g-1(x=0)、76.8mA·h·g-1(x=0.1)、0.7mA·h·g-1(x=0.3)、2.3mA·h·g-1(x=0.5)、21.2mA·h·g-1(x ═ 0.7) and 4.5mA · h · g-1(x ═ 1), the capacity retention ratio was 97.62%, 81.32%, 1.45%, 3.27%, 11.23%, and 4.52%.
Comparative example two:
the comparative example was the same as example one except that the kind of the conductive agent was different.
S1.1 Life from example one1-xVxPO4F1-δOδMixing the pure phase powder and acetylene black according to the mass ratio of 7:2, and performing ball milling to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder. LiFe thus obtained1-xVxPO4F1-δOδWhen the battery is cycled for 30 times, the discharge capacity is 65.89 mA.h.g-1(x=0)、56.72mA·h·g-1(x=0.1)、0.1mA·h·g-1(x=0.3)、1.1mA·h·g-1(x=0.5)、11.7mA·h·g-1(x ═ 0.7) and 2.5mA · h · g-1(x ═ 1), the capacity retention was 97.62%, 81.32%, 1.45%, 3.27%, 11.23%, and 4.52%, and the electrochemical performance tested was very poor.

Claims (10)

1. A preparation method of a fluoxaphosphate lithium ion battery material, wherein x is more than 0 and less than 1, and delta is less than or equal to 0.4; the method is characterized by comprising the following steps:
1) according to VPO4Weighing the following components in a metering ratio: grinding and mixing vanadium source and phosphorus source raw materials, calcining for 3-8 hours in inert gas at 200-400 ℃, and cooling to room temperature to obtain powder;
2) grinding and mixing the powder obtained in the step 1) for 0.5-2 hours, calcining the mixture in inert gas at 700-900 ℃ for 4-10 hours, and cooling the mixture to room temperature to obtain VPO4A powder as a main phase;
3)LiFe1-xVxPO4F1-δOδpreparation of powder: according to LiFe1-xVxPO4F1-δOδWeighing ferric phosphate, lithium fluoride powder and the vanadium phosphate prepared in the step 2) according to a metering ratio, and grinding to obtain Li-Fe-V-P-O-F precursor powder, wherein the molar weight of the lithium fluoride powder is 1-1.05 times of the total molar weight of the ferric phosphate and the vanadium phosphate powder;
4) calcining Li-Fe-V-P-O-F precursor powder in inert gas at the temperature of 575-675 ℃ for 1.5-6 hours, and grinding to obtain LiFe1-xVxPO4F1-δOδA pure phase powder.
2. The method of claim 1, wherein in step 1): the vanadium source is one of vanadium trioxide or vanadium pentoxide.
3. The method of claim 1, wherein in step 1): the phosphorus source is one of diammonium hydrogen phosphate or phosphorous acid.
4. The method of claim 1, wherein x is 0.1, 0.3, 0.5, or 0.7.
5. The method of claim 1, wherein the inert gas is argon or nitrogen.
6. A preparation method of a fluoride oxygen phosphate lithium ion battery positive plate is characterized by comprising the following steps:
1) reacting the LiFe of any one of claims 1 to 51-xVxPO4F1-δOδMixing the pure-phase powder and the nano conductive carbon according to the mass ratio of 3: 1-8: 1, and performing ball milling to obtain LiFe1-xVxPO4F1-δOδC carbon-coated powder;
2) mixing LiFe1-xVxPO4F1-δOδPowder of/C and polyvinylidene fluorideMixing ethylene according to the mass ratio of 9: 1-9.5: 0.5, dissolving the mixture in N-methyl pyrrolidone, stirring the mixture until the viscosity is 3000-6000 mPa.s, coating the mixture on an aluminum foil, and drying the aluminum foil in vacuum to obtain LiFe1- xVxPO4F1-δOδAnd (4) a positive plate.
7. The method of claim 6, wherein in step 1): the nano conductive carbon is a carbon particle, a carbon nanotube or a graphene carbon source with a size of less than 100nm in at least one direction.
8. The method of claim 6, wherein in step 1): the ball milling time is 4-8 hours.
9. The method of claim 6, wherein in step 2): LiFe1-xVxPO4F1-δOδThe mass ratio of the/C powder to the N-methyl pyrrolidone is 1: 7-1: 9.
10. A lithium ion battery, characterized in that it comprises a positive electrode sheet as defined in any one of claims 6 to 9.
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