CN109244397A - Phosphoric acid vanadium lithium/lithium manganese phosphate cladding lithium-rich manganese-based anode material preparation method - Google Patents
Phosphoric acid vanadium lithium/lithium manganese phosphate cladding lithium-rich manganese-based anode material preparation method Download PDFInfo
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- CN109244397A CN109244397A CN201810999819.1A CN201810999819A CN109244397A CN 109244397 A CN109244397 A CN 109244397A CN 201810999819 A CN201810999819 A CN 201810999819A CN 109244397 A CN109244397 A CN 109244397A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Phosphoric acid vanadium lithium/lithium manganese phosphate cladding lithium-rich manganese-based anode material preparation method, comprising the following steps: (1) preparation of lithium-rich manganese-based anode material；(2) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate presoma；(3) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate material.The present invention coats phosphoric acid vanadium lithium/lithium manganese phosphate in lithium-rich manganese-based anode material surface in situ by spray drying, after high-temperature process under reducing atmosphere, forms phosphoric acid vanadium lithium/lithium manganese phosphate and coats lithium-rich manganese-based anode material.Its surface coated phosphoric acid vanadium lithium/lithium manganese phosphate material layer, for the cenotype generated during covered composite yarn, with stable structure and faster lithium ion transport rate, the material after cladding has shown excellent chemical property.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery lithium-rich manganese base, more particularly, to a kind of phosphoric acid
Vanadium lithium/lithium manganese phosphate cladding lithium-rich manganese-based anode material preparation method.
Background technique
Lithium ion battery has the characteristics that energy density is high, has extended cycle life, it is considered to be the following electric car and mixing
The important green energy resource in power car field.But the lower specific volume metric density of lithium ion battery is not able to satisfy current use still
Demand, therefore researching and developing, there is the anode material for lithium-ion batteries of height ratio capacity density to become the development of power type ev industry
It is crucial.
Lithium-rich manganese-based anode material [xLi2MnO3·(1-x)LiMO2 (0<x< 1)] due to height ratio capacity, low cost, environment
The advantages that friendly and receive significant attention.But the irreversible capacity loss for the first time of such material is serious, capacity declines in cyclic process
Subtract the disadvantages of poor with high rate performance, greatly hinders its marketing development.The low reason of first charge-discharge efficiency be its for the first time
Li when charging to 4.5V, in transition metal layer in its layer structure+With Li2O deviates from only from structure, while with O2
Generation and structure rearrangement, and the Li that this part is deviate from only2O can not be returned in lattice, produce biggish irreversible appearance
Amount and lower first charge-discharge efficiency.In addition, in charge and discharge process, part Li+Vacancy is occupied by metal ion, leads to Li+
Diffusion admittance is obstructed, and material recurring structure is reset, and is changed from layer structure to spinel-like structural, therefore lead to cycle performance
Decline.In material manganese element be+4 valences, conductive capability and ion diffusion rates are low, thus lithium-rich manganese base material high rate performance compared with
Difference.
In order to solve problem above, modification technology most effective at present is surface cladding.Common surface coats material
Material is metal oxide, metal fluoride and metal phosphate.Metal phosphate is because it is with preferable thermodynamic stability
A kind of ideal covering material.Compared to LiFePO4 (LiFePO4), NASICON type phosphoric acid vanadium lithium [Li3V2(PO4)3] theoretical
Specific capacity height (197mAh/g) has three-dimensional lithium ion diffusion admittance, is a kind of fast ion conducting material, has shown outstanding
High rate performance.Lithium manganese phosphate (LiMnPO4) have the advantages that thermal stability is good, highly-safe.By two kinds of traditional phosphate
It is that positive electrode and lithium-rich manganese base material are prepared into three-phase composite material, utilizes the outstanding ionic conductivity of phosphoric acid vanadium lithium, height
Theoretical specific capacity and the good advantage of lithium manganese phosphate thermal stability are effectively improved lithium-rich manganese base material structure in charge and discharge process and turn
Become the defect low with lithium ion diffusion rate, promotes the chemical property of composite material.Moreover, phosphoric acid vanadium lithium also have compared with
Wide electrochemical window (3.0-4.8V) and lithium manganese phosphate electrochemistry platform (4.1V) with higher are contributed for composite material
Higher electrochemistry capacitance out.In addition, phosphoric acid vanadium lithium and lithium manganese phosphate are faintly acid, by its with lithium-rich manganese base material it is compound after,
The residual lithium content of material surface and basicity can be reduced, the cycle performance of material is further promoted.
CN105355819A discloses the preparation method of a kind of lithium-rich manganese-based anode material and phosphoric acid vanadium lithium mixing material, but
The lithium-rich manganese-based base anode material cyclic process capacity of stratiform and voltage attenuation cannot fundamentally be solved by being that simple physics is compound
The disadvantages of.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide phosphoric acid vanadium lithium/lithium manganese phosphate cladding
The preparation method of lithium-rich manganese-based anode material improves rich on the basis of solving lithium-rich manganese-based anode material cyclical stability difference
Lithium manganese-based anode material specific discharge capacity.
The technical solution used to solve the technical problems of the present invention is that phosphoric acid vanadium lithium/lithium manganese phosphate cladding is lithium-rich manganese-based just
The preparation method of pole material, comprising the following steps:
(1) preparation of lithium-rich manganese-based anode material: lithium-rich manganese-based presoma is fully ground with lithium source and is mixed, in air atmosphere
It calcines, arrives lithium-rich manganese-based anode material after natural cooling；
(2) preparation of the presoma of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate: according to molar ratio by a certain proportion of lithium source, vanadium
Source, phosphorus source, manganese source and carbon source ultrasonic disperse in deionized water, obtain evenly dispersed solution a, and solution a is phosphoric acid vanadium
The solution of lithium, lithium manganese phosphate；According to the quality of phosphoric acid vanadium lithium, lithium manganese phosphate in solution a, by phosphoric acid vanadium lithium, lithium manganese phosphate it is total
Quality: lithium-rich manganese-based anode material=1-10:100 ratio weighs lithium-rich manganese-based anode material obtained by step (1), by rich lithium
Manganese-based anode material is scattered in deionized water, obtains solution b；Under stiring, solution a is added into solution b, is mixed
Liquid；Mixed liquor is spray-dried, can be prepared by the presoma of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate；
(3) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate material: by lithium-rich manganese-based@phosphoric acid vanadium lithium/phosphorus obtained by step (2)
The presoma of sour manganese lithium is calcined in reducing atmosphere, coats rich lithium manganese after natural cooling to get to phosphoric acid vanadium lithium/lithium manganese phosphate
Base anode material.
The phosphoric acid vanadium lithium of the present invention/lithium manganese phosphate coats lithium-rich manganese-based anode material, the i.e. rich lithium manganese of surface covered composite yarn
Base anode material, can be expressed by the following formula:xLi2MnO3·(1-x)LiMO2@y[Li3V2(PO4)3·LiMn(PO4)](0 < x
< 1,0 < y≤ 10%), wherein M is selected from least one of Ni, Co, Mn, Cr, Fe, Zn, Al, Mg, Cd element, and y is indicated
Covering amount, i.e. phosphoric acid vanadium lithium/lithium manganese phosphate Li3V2(PO4)3·LiMn(PO4) gross mass and lithium-rich manganese-based anode materialxLi2MnO3·(1-x)LiMO2Mass ratio.
Further, in step (1), lithium-rich manganese-based presoma is Mn0.674Ni0.163Co0.163CO3、Mn0.674Ni0.163Co0.163
(OH)2、Mn0.667Ni0.166Co0.166CO3、Mn0.667Ni0.166Co0.166(OH)2、Mn0.75Ni0.25(OH)2、Mn0.75Ni0.25CO3、
Mn4/6Ni1/6Co1/6CO3At least one of.
Further, in step (1) neutralization procedure (2), lithium source be lithium carbonate, lithium nitrate, lithium acetate, in lithium hydroxide extremely
Few one kind.Its hydrate can also be used in lithium source.
Further, in step (1), calcining is carried out in two steps, first in 400 ~ 550 DEG C of calcining 4-8h, then at 700 ~ 1100 DEG C
Calcine 8 ~ 20h.
Further, in step (1), in lithium source the amount of the substance of contained lithium in lithium-rich manganese-based presoma Ni, Co, Mn it is total
The ratio of the amount of substance is 1.5-1.6 ︰ 1.
Further, in step (2), the P elements in elemental lithium, phosphorus source in the lithium source, the vanadium in vanadium source, manganese
The molar ratio of the carbon in manganese element, carbon source in source is 4:4:2:1:2-3.4.
Further, the carbon source in step (2) is glucose, sucrose, oxalic acid, ethanedioic acid, citric acid, soluble starch, resists
At least one of bad hematic acid.Suitable carbon coating can be improved the conductive capability of material, promote active material to play bigger
Capacity.
Further, the vanadium source in step (2) is at least one of vanadic anhydride, metavanadic acid ammonia.
Further, the phosphorus source in step (2) is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate.
Further, the manganese source in step (2) is manganese oxide, manganese dioxide, manganese carbonate, at least one in manganese nitrate hexahydrate
Kind.
Further, the frequency of ultrasonic disperse is 40 ~ 60kHz in step (2), and temperature is 20 ~ 40 DEG C, and the time is 2 ~ 10h.
Further, mixed liquor is spray-dried with the feed speed of 5-20mL/min, at 200 ~ 300 DEG C in step (2).
Further, in step (3), reducing atmosphere is the gaseous mixture of helium, nitrogen or argon atmosphere or argon gas and hydrogen
Atmosphere.
Further, in step (3), calcination temperature is 500 ~ 900 DEG C, and calcination time is 5 ~ 25h.
The present invention prepares phosphoric acid vanadium lithium/lithium manganese phosphate in-stiu coating lithium-rich manganese-based anode material for the first time, it is intended to improve material
Specific discharge capacity and cyclical stability in cyclic process.
The present invention coats phosphoric acid vanadium lithium/lithium manganese phosphate in lithium-rich manganese-based anode material surface in situ by spray drying,
Under reducing atmosphere after high-temperature process, forms phosphoric acid vanadium lithium/lithium manganese phosphate and coat lithium-rich manganese-based anode material.Its is surface coated
Phosphoric acid vanadium lithium/lithium manganese phosphate material layer is the cenotype generated during covered composite yarn, with stable structure and faster
Lithium ion transport rate, the material after cladding have shown excellent chemical property.
Compared with prior art, the present invention has the following advantages:
1) phosphoric acid vanadium lithium prepared by the present invention/lithium manganese phosphate cladding lithium-rich manganese-based anode material is by spray drying, in rich lithium manganese
Phosphoric acid vanadium lithium/lithium manganese phosphate the clad of one layer of even compact of growth in situ on base.
2) present invention combines lithium-rich manganese-based anode material with phosphoric acid vanadium lithium/lithium manganese phosphate advantage, mutually inhibits it
Disadvantage obtains the good phosphoric acid vanadium lithium of concertedness/lithium manganese phosphate cladding lithium-rich manganese-based anode material.Lithium-rich manganese-based anode material table
Phosphoric acid vanadium lithium/lithium manganese phosphate the clad of one layer of even compact of face growth in situ.The appearance of cenotype consumes lithium-rich manganese-based anode
The Li of " more than needed " in material+, reduce the Li of these " more than needed "+With Li2The form of O is from the irreversible abjection in structure, to drop
The low loss of irreversible capacity for the first time.On the other hand there is quick Li+The phosphoric acid vanadium lithium in channel/lithium manganese phosphate cenotype is in rich lithium
Mn-based material surface forms stable clad, and lithium-rich manganese-based ionic mobility can be improved, and resists the erosion of electrolyte, thus
Improve the cyclical stability of material.Phosphoric acid vanadium lithium and lithium manganese phosphate are faintly acid, by its with lithium-rich manganese base material it is compound after, can be with
The residual lithium content of material surface and basicity are reduced, the cycle performance of material is further promoted.
3) in the present invention, phosphoric acid vanadium lithium/lithium manganese phosphate has wider electrochemical window (3.0-4.8V), higher electrification
Platform is learned, the chemical property of material can be effectively improved.
Detailed description of the invention
Fig. 1 is the SEM figure that phosphoric acid vanadium lithium/lithium manganese phosphate prepared by the embodiment of the present invention 1 coats lithium-rich manganese-based anode material；
Fig. 2 is the SEM figure of the lithium-rich manganese-based anode material of comparative example 1 of the present invention preparation；
Fig. 3 is the TEM figure that phosphoric acid vanadium lithium/lithium manganese phosphate prepared by the embodiment of the present invention 1 coats lithium-rich manganese-based anode material；
Fig. 4 is that phosphoric acid vanadium lithium/lithium manganese phosphate cladding lithium-rich manganese-based anode material prepared by the embodiment of the present invention 1 and comparative example 1 are rich
Charging and discharging curve comparison diagram of the button cell of lithium manganese-based anode material assembling under 0.2C discharge-rate.
Specific embodiment
In order to be further understood to the present invention, the preferred embodiment of the invention is made below with reference to embodiment further
Description, protection scope of the present invention is not limited to the examples, and protection scope of the present invention is determined by claims
It is fixed.
Embodiment 1
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol4/6Ni1/6Co1/6CO3With 0.1302molLiOH ﹒ H2O carries out hand mill mixing
(crossing lithium amount is 5%), milling time 2h；Raw material is put into crucible, is placed in Muffle furnace, in air atmosphere, first 500 DEG C of pre-sinterings
6h, then in 900 DEG C of sintering 10h, heating rate is 5 DEG C/min, until furnace temperature grinds 1h, partial size after grinding after being cooled to room temperature
For 10-25 μm to get lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2。
(2) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate presoma: LiOHH is weighed2O
(0.000704mol)、V2O5(0.000176mol)、Mn(NO3)2·6H2O(0.000176mol)、C6H12O6
(0.0000875mol)、(NH4)2HPO4(0.000704mol) controls elemental lithium, the P elements in phosphorus source, vanadium source in lithium source
In vanadium, the manganese element in manganese source, the carbon in carbon source molar ratio be 4:4:2:1:3, be scattered in deionization
In water, ultrasonic 4h, the frequency of ultrasonic disperse is 40kHz, and temperature is 20 DEG C, obtains evenly dispersed mixed liquor a；Solution a be containing
The solution of phosphoric acid vanadium lithium, lithium manganese phosphate；Phosphoric acid vanadium lithium in solution a, lithium manganese phosphate quality be 0.1000g, by phosphoric acid vanadium lithium, phosphorus
The gross mass of sour manganese lithium: lithium-rich manganese-based anode material=1:100 ratio, 10.0000g step (1) gained is lithium-rich manganese-based just
Pole material is dissolved in deionized water, obtains mixed liquor b；Under stirring, solution a is added into solution b, is mixed
Liquid；Mixed liquor is spray-dried, the temperature of spray drying is 250 DEG C, and charging rate 5mL/min can be prepared by rich lithium
Manganese base@phosphoric acid vanadium lithium/lithium manganese phosphate presoma；
(3) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/manganese-lithium phosphate anode material
With the heating rate of 5 DEG C/min, the presoma of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate obtained by step (2) is placed in
750 DEG C are sintered 12h under an argon atmosphere, and furnace cooling to room temperature obtains phosphoric acid vanadium lithium/lithium manganese phosphate and coats lithium-rich manganese-based anode
Material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2@1%[Li3V2(PO4)3·LiMn(PO4)]。
The assembling of battery: it is lithium-rich manganese-based just to weigh phosphoric acid vanadium lithium obtained by the 0.4000g embodiment of the present invention/lithium manganese phosphate cladding
Pole material is added 0.0500g conductive carbon black and makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in aluminium foil
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled is in 2.0~4.8V voltage range, and under 0.05C multiplying power, the gram volume that discharges for the first time is 394
mAh/g。
Phosphoric acid vanadium lithium/lithium manganese phosphate cladding lithium-rich manganese-based anode material and lithium-rich manganese-based anode in comparative example 1 in embodiment 1
Cyclic curve comparison of the material under 0.2C discharge-rate, as shown in Figure 4, it is seen that the lithium-rich manganese-based anode material electric discharge after cladding
Specific capacity is higher than uncoated lithium-rich manganese-based anode material.
Embodiment 2
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.1680mol4/6Ni1/6Co1/6CO3With 0.1302molLi2CO3Carry out hand mill mixing (mistake
Lithium amount is 5%) milling time 3h；Raw material is put into crucible, is placed in Muffle furnace, in air atmosphere, is first pre-sintered at 500 DEG C
6h, then in 950 DEG C of sintering 10h, heating rate is 5 DEG C/min, until furnace temperature grinds 1.5h, grain after grinding after being cooled to room temperature
Diameter is 10-25 μm to get lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2。
(2) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate presoma: LiOHH is weighed2O
(0.001408mol)、V2O5(0.000352mol)、MnO2 (0.000352mol)、C6H12O6(0.000175mol)、(NH4)2HPO4(0.001408mol) controls elemental lithium, the P elements in phosphorus source, the vanadium in vanadium source, the manganese in manganese source in lithium source
The molar ratio of carbon in element, carbon source is 4:4:2:1:3, is scattered in deionized water, ultrasonic 4h, ultrasonic disperse
Frequency is 40kHz, and temperature is 20 DEG C, obtains evenly dispersed mixed liquor a；Solution a be phosphoric acid vanadium lithium, lithium manganese phosphate it is molten
Liquid；Phosphoric acid vanadium lithium in solution a, lithium manganese phosphate quality be 0.2000g, by the gross mass of phosphoric acid vanadium lithium, lithium manganese phosphate: rich lithium manganese
Lithium-rich manganese-based anode material obtained by 10.0000g step (1) is dissolved in deionized water by base anode material=2:100 ratio,
Obtain mixed liquor b；Under stirring, solution a is added into solution b, obtains mixed liquor；Mixed liquor is done by spraying
Dry, the temperature of spray drying is 250 DEG C, charging rate 5mL/min, can be prepared by lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate
Presoma；
(3) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/manganese-lithium phosphate anode material
With the heating rate of 5 DEG C/min, the presoma of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate obtained by step (2) is placed in
700 DEG C are sintered 15h under an argon atmosphere, and after furnace cooling to room temperature, it is lithium-rich manganese-based just to obtain phosphoric acid vanadium lithium/lithium manganese phosphate cladding
Pole material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2@2%[Li3V2(PO4)3·LiMn(PO4)]。
The assembling of battery: phosphoric acid vanadium lithium obtained by the 0.4000g embodiment of the present invention/lithium manganese phosphate cladding lithium-rich manganese-based anode material is weighed
Material is added 0.0500g conductive carbon black and makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated on aluminium foil and makes
It is diaphragm, 1mol/L LiPF with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box at positive plate6/EC:
DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled is in 2.0~4.8V voltage range, and under 0.05C multiplying power, the gram volume that discharges for the first time is 383
mAh/g。
Embodiment 3
The present embodiment the following steps are included:
(1) preparation of lithium-rich manganese-based anode material
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol4/6Ni1/6Co1/6CO3With 0.1302molLiOH ﹒ H2O carries out hand mill mixing
(crossing lithium amount is 5%), milling time 2h；Raw material is put into crucible, Muffle furnace is placed in, first in 500 DEG C of pre-sintering 5h, then 900
DEG C sintering 10h, heating rate is 5 DEG C/min, until furnace temperature grinds 1h after being cooled to room temperature, partial size is 10-25 μm after grinding, i.e.,
Obtain lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2。
(2) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate presoma: LiOHH is weighed2O(0.0040mol)、
V2O5(0.0010mol)、Mn(NO3)2·6H2O(0.0010mol)、C6H12O6(0.0005mol)、 (NH4)2HPO4
(0.0040mol), control lithium source in elemental lithium, the P elements in phosphorus source, the vanadium in vanadium source, the manganese element in manganese source,
The molar ratio of carbon in carbon source is 4:4:2:1:3, is scattered in deionized water, ultrasonic 4h, the frequency of ultrasonic disperse
For 40kHz, temperature is 20 DEG C, obtains evenly dispersed mixed liquor a；Solution a is the solution of phosphoric acid vanadium lithium, lithium manganese phosphate；It is molten
Phosphoric acid vanadium lithium in liquid a, lithium manganese phosphate quality be 0.5650g, by the gross mass of phosphoric acid vanadium lithium, lithium manganese phosphate: it is lithium-rich manganese-based just
Pole material=5.65:100 ratio, 10.0000g lithium-rich manganese-based anode material is dissolved in deionized water, obtains mixed liquor b；
Under stirring, solution a is added into solution b, obtains mixed liquor；Mixed liquor is spray-dried, spray drying
Temperature is 250 DEG C, charging rate 5mL/min, can be prepared by the presoma of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate；
(3) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/manganese-lithium phosphate anode material
With the heating rate of 5 DEG C/min, the presoma of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate obtained by step (2) is placed in
700 DEG C are sintered 12h under an argon atmosphere, and after furnace cooling to room temperature, it is lithium-rich manganese-based just to obtain phosphoric acid vanadium lithium/lithium manganese phosphate cladding
Pole material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2@5.65%[Li3V2(PO4)3·LiMn(PO4)]。
The assembling of battery: it is lithium-rich manganese-based just to weigh phosphoric acid vanadium lithium obtained by the 0.4000g embodiment of the present invention/lithium manganese phosphate cladding
Pole material is added 0.0500g conductive carbon black and makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in aluminium foil
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled is in 2.0~4.8V voltage range, and under 0.05C multiplying power, the gram volume that discharges for the first time is 386mAh/
g。
Comparative example 1:
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol4/6Ni1/6Co1/6CO3With 0.1302molLiOH ﹒ H2O carries out hand mill mixing
(crossing lithium amount is 5%), milling time 2h；Raw material is put into crucible, is placed in Muffle furnace, in air atmosphere, first 500 DEG C of pre-sinterings
6h, then in 900 DEG C of sintering 10h, heating rate is 5 DEG C/min, until furnace temperature grinds 1h, partial size after grinding after being cooled to room temperature
For 10-25 μm to get lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2。
The assembling of battery: weighing lithium-rich manganese-based anode material obtained by the 0.4000g embodiment of the present invention, and 0.0500g is added and leads
Electrical carbon is black to make conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated on aluminium foil anode is made after mixing
Piece is diaphragm, 1mol/L LiPF with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box6/ EC:DMC(body
Product is than 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled is in 2.0~4.8V voltage range, and under 0.05C multiplying power, the gram volume that discharges for the first time is 310
mAh/g。
Comparative example 2:
Weigh the lithium-rich manganese-based presoma Mn of 0.1680mol4/6Ni1/6Co1/6CO3With 0.1302molLi2CO3Carry out hand mill mixing (mistake
Lithium amount is 5%) milling time 3h；Raw material is put into crucible, is placed in Muffle furnace, in air atmosphere, is first pre-sintered at 500 DEG C
6h, then in 950 DEG C of sintering 10h, heating rate is 5 DEG C/min, until furnace temperature grinds 1.5h, grain after grinding after being cooled to room temperature
Diameter is 10-25 μm to get lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2。
The assembling of battery: weighing lithium-rich manganese-based anode material material obtained by the 0.4000g embodiment of the present invention, is added
0.0500g conductive carbon black makees conductive agent and 0.0500g PVDF(Kynoar) make binder, it is coated in aluminium foil after mixing
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled is in 2.0~4.8V voltage range, and under 0.05C multiplying power, the gram volume that discharges for the first time is 317mAh/
g。
Comparative example 3:
Weigh the lithium-rich manganese-based presoma Mn of 0.0840mol4/6Ni1/6Co1/6CO3With 0.1302molLiOH ﹒ H2O carries out hand mill mixing
(crossing lithium amount is 5%), milling time 2h；Raw material is put into crucible, Muffle furnace is placed in, first in 500 DEG C of pre-sintering 5h, then 900
DEG C sintering 10h, heating rate is 5 DEG C/min, until furnace temperature grinds 1h after being cooled to room temperature, partial size is 10-25 μm after grinding, i.e.,
Obtain lithium-rich manganese-based anode material 0.5Li2MnO3·0.5Li(Ni1/3Co1/3Mn1/3)O2。
The assembling of battery: weighing lithium-rich manganese-based anode material material obtained by the 0.8000g embodiment of the present invention, is added
0.1000g conductive carbon black makees conductive agent and 0.1000g PVDF(Kynoar) make binder, it is coated in aluminium foil after mixing
On positive plate is made, be diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box
LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
The battery assembled is in 2.0~4.8V voltage range, and under 0.05C multiplying power, the gram volume that discharges for the first time is 308
mAh/g。
To sum up, the present invention is prepared for a kind of phosphoric acid vanadium lithium/phosphoric acid with high specific discharge capacity and good circulation performance
The lithium-rich manganese-based base anode material of manganese lithium cladding.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. phosphoric acid vanadium lithium/lithium manganese phosphate cladding lithium-rich manganese-based anode material preparation method, which is characterized in that including following step
It is rapid:
(1) preparation of lithium-rich manganese-based anode material: lithium-rich manganese-based presoma is fully ground with lithium source and is mixed, in air atmosphere
It calcines, arrives lithium-rich manganese-based anode material after natural cooling；
(2) preparation of the presoma of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate: according to molar ratio by lithium source, vanadium source, phosphorus source, manganese
Source and carbon source ultrasonic disperse in deionized water, obtain evenly dispersed solution a, solution a is phosphoric acid vanadium lithium, lithium manganese phosphate
Solution；According to the quality of phosphoric acid vanadium lithium, lithium manganese phosphate in solution a, by the gross mass of phosphoric acid vanadium lithium, lithium manganese phosphate: rich lithium manganese
Base anode material=1-10:100 ratio weighs lithium-rich manganese-based anode material obtained by step (1), by lithium-rich manganese-based anode material
It is scattered in deionized water, obtains solution b；Under stiring, solution a is added into solution b, obtains mixed liquor；By mixed liquor
It is spray-dried, can be prepared by the presoma of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate；
(3) preparation of lithium-rich manganese-based@phosphoric acid vanadium lithium/lithium manganese phosphate material: by lithium-rich manganese-based@phosphoric acid vanadium lithium/phosphorus obtained by step (2)
The presoma of sour manganese lithium is calcined in reducing atmosphere, coats rich lithium manganese after natural cooling to get to phosphoric acid vanadium lithium/lithium manganese phosphate
Base anode material.
2. phosphoric acid vanadium lithium according to claim 1/lithium manganese phosphate coats lithium-rich manganese-based anode material, which is characterized in that by
Following general formula indicates:xLi2MnO3·(1-x)LiMO2@y[Li3V2(PO4)3·LiMn(PO4)],0 < x< 1,0 < y≤ 10%,
Wherein, M is selected from least one of Ni, Co, Mn, Cr, Fe, Zn, Al, Mg, Cd element, and y indicates covering amount, i.e. vanadium phosphate
Lithium/lithium manganese phosphate gross mass and lithium-rich manganese-based anode material mass ratio.
3. phosphoric acid vanadium lithium according to claim 1 or 2/lithium manganese phosphate coats lithium-rich manganese-based anode material, which is characterized in that
In step (1), lithium-rich manganese-based presoma is Mn0.674Ni0.163Co0.163CO3、Mn0.674Ni0.163Co0.163(OH)2、
Mn0.667Ni0.166Co0.166CO3、Mn0.667Ni0.166Co0.166(OH)2、Mn0.75Ni0.25 (OH)2、Mn0.75Ni0.25CO3、Mn4/ 6Ni1/6Co1/6CO3At least one of.
4. phosphoric acid vanadium lithium according to claim 1 or 2/lithium manganese phosphate coats lithium-rich manganese-based anode material, which is characterized in that
In step (1) neutralization procedure (2), lithium source is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide；Or it uses
At least one of its hydrate.
5. phosphoric acid vanadium lithium according to claim 1 or 2/lithium manganese phosphate coats lithium-rich manganese-based anode material, which is characterized in that
In step (1), calcining is carried out in two steps, first in 400 ~ 550 DEG C of calcining 4-8h, then in 700 ~ 1100 DEG C of 8 ~ 20h of calcining.
6. phosphoric acid vanadium lithium according to claim 1 or 2/lithium manganese phosphate coats lithium-rich manganese-based anode material, which is characterized in that
In step (1), in lithium source in the amount of the substance of contained lithium and lithium-rich manganese-based presoma the amount of the total material of Ni, Co, Mn ratio
For 1.5-1.6 ︰ 1.
7. phosphoric acid vanadium lithium according to claim 1 or 2/lithium manganese phosphate coats lithium-rich manganese-based anode material, which is characterized in that
The P elements in elemental lithium, phosphorus source, the vanadium in vanadium source, the manganese element in manganese source, carbon in step (2), in the lithium source
The molar ratio of carbon in source is 4:4:2:1:2-3.4.
8. phosphoric acid vanadium lithium according to claim 1 or 2/lithium manganese phosphate coats lithium-rich manganese-based anode material, which is characterized in that
In step (2), carbon source is glucose, sucrose, oxalic acid, ethanedioic acid, citric acid, soluble starch, at least one in ascorbic acid
Kind；Vanadium source is at least one of vanadic anhydride, metavanadic acid ammonia；Phosphorus source is ammonium dihydrogen phosphate, in diammonium hydrogen phosphate, ammonium phosphate
At least one；Manganese source is at least one of manganese oxide, manganese dioxide, manganese carbonate, manganese nitrate hexahydrate.
9. phosphoric acid vanadium lithium according to claim 1 or 2/lithium manganese phosphate coats lithium-rich manganese-based anode material, which is characterized in that
In step (2), the frequency of ultrasonic disperse is 40 ~ 60kHz, and temperature is 20 ~ 40 DEG C, and the time is 2 ~ 10h；Mixed liquor is with 5-20mL/
The feed speed of min is spray-dried at 200 ~ 300 DEG C.
10. phosphoric acid vanadium lithium according to claim 1 or 2/lithium manganese phosphate coats lithium-rich manganese-based anode material, feature exists
In in step (3), reducing atmosphere is the mixed atmosphere of helium, nitrogen or argon atmosphere or argon gas and hydrogen；Calcination temperature
It is 500 ~ 900 DEG C, calcination time is 5 ~ 25h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518206A (en) * | 2019-08-22 | 2019-11-29 | 湖北锂诺新能源科技有限公司 | Manganese phosphate vanadium lithium and carbon coat the preparation method of nickel cobalt manganese aluminium composite positive pole altogether |
| CN111082009A (en) * | 2019-12-17 | 2020-04-28 | 中南大学 | Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof |
| CN115304043A (en) * | 2022-04-25 | 2022-11-08 | 深圳市德方创域新能源科技有限公司 | Composite phosphate anode material and preparation method and application thereof |
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2018
- 2018-08-30 CN CN201810999819.1A patent/CN109244397A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518206A (en) * | 2019-08-22 | 2019-11-29 | 湖北锂诺新能源科技有限公司 | Manganese phosphate vanadium lithium and carbon coat the preparation method of nickel cobalt manganese aluminium composite positive pole altogether |
| CN111082009A (en) * | 2019-12-17 | 2020-04-28 | 中南大学 | Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof |
| CN111082009B (en) * | 2019-12-17 | 2021-04-09 | 中南大学 | Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof |
| CN115304043A (en) * | 2022-04-25 | 2022-11-08 | 深圳市德方创域新能源科技有限公司 | Composite phosphate anode material and preparation method and application thereof |
| CN115304043B (en) * | 2022-04-25 | 2023-12-29 | 深圳市德方创域新能源科技有限公司 | Composite phosphate positive electrode material, preparation method and application thereof |
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