CN106450304A - Lithium manganese phosphate composite cathode material and preparation method and application thereof - Google Patents
Lithium manganese phosphate composite cathode material and preparation method and application thereof Download PDFInfo
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- 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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- C01B25/00—Phosphorus; Compounds thereof
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- C01B25/26—Phosphates
- C01B25/265—General methods for obtaining phosphates
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- 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 discloses a lithium manganese phosphate composite cathode material and a preparation method and application thereof. According to the method, lithium manganese phosphate is used as a matrix, and TiC and a dopant wrap the outside of the matrix to obtain the lithium manganese phosphate composite cathode material. The method is gentle in reaction condition, simple in process, convenient to operate, low in production cost, and simple and controllable in synthesis path; the morphology and the size of the material are easily micro-regulated; the material is suitable for being produced on a large scale; and the prepared lithium manganese phosphate composite cathode material is good in electrical conductivity, high in conductivity, high in capacity and good in rate capability.
Description
Technical field
The present invention relates to new energy materialses preparation and application are and in particular to lithium manganese phosphate composite positive pole and its preparation side
Method and application.
Background technology
Lithium ion battery as a kind of novel energy-storing power supply, have that operating voltage is high, energy density is high, memory-less effect and
The advantages of low discharge rate, now it is widely used in the fields such as electric motor car, communication equipment, energy storage device, Aero-Space.Wherein, electricity
Pond positive pole plays an important role to the performance of battery.
The anode material of lithium battery of commercialization mainly has cobalt acid lithium LiCoO2, LiMn2O4 LiMn2O4, nickle cobalt lithium manganate
LiNi1/3Co1/3Mn1/3O2With LiFePO4 LiFePO4Four kinds.Wherein, cobalt acid lithium LiCoO2Due to expensive, resource scarcity,
The shortcomings of security difference, hampers the application on dynamic lithium battery；LiMn2O4 LiMn2O4It is the lithium electricity following cobalt acid lithium commercialization closely
Pond positive electrode, its cycle performance has obtained certain improvement, but high temperature cyclic performance is not still resolved, and limits it dynamic
The application of power battery especially electric vehicle power sources aspect；Nickle cobalt lithium manganate LiNi1/3Co1/3Mn1/3O2With LiFePO4 LiFePO4Three
The impetus of first material substituted greatly cobalt acid lithium in recent years, but this can not solve cost, toxicity and the security of lithium battery at all
Problem.
Lithium manganese phosphate has low cost, before the wide feature of raw material sources has a wide range of applications on anode material of lithium battery
Scape, the preparation method of current lithium manganese phosphate has solid phase method and microwave-hydrothermal method etc., but root it has been reported that they all have operation numerous
Trivial, the shortcomings of synthesis step is more, and the manganese-lithium phosphate anode material prepared has deadly defect, its poorly conductive, its electricity
Conductance is low, hardly results in commercial applications.
Content of the invention
An object of the present invention is to provide process is simple, easy to operate controlled, low production cost lithium manganese phosphate multiple
Close the preparation method of positive electrode.
The second object of the present invention is to provide the good conductivity being prepared from by said method, electrical conductivity height, capacity high, again
The good lithium manganese phosphate composite positive pole of rate performance.
The third object of the present invention is to provide application in lithium battery anode for the above-mentioned lithium manganese phosphate composite positive pole.
The preparation method of the lithium manganese phosphate composite positive pole that the present invention provides includes：
(1) Ti and C powder is mixed to prepare mixture, then ball milling, drying, shaping, calcining, cooling, pulverizing is obtained TiC；
(2) lithium source, manganese source, phosphorus source are added dispersed with stirring in dispersant, be subsequently added into alloy and described TiC carries out ball
Mill is to be obtained ball milling slurry；
(3) described ball milling slurry is dried and presoma is obtained, then ball milling, pulverizing, pressed compact are to be obtained base substrate；
(4) described base substrate is placed in inert gas carry out roasting, cooling, pulverizing, jolt ramming be obtained lithium manganese phosphate be combined
Positive electrode；
Wherein, elemental lithium in described lithium source, manganese element in described manganese source, in phosphorus source the amount of material of P elements ratio
For 0.85-1.25：0.9-1.1：0.98-1.02；On the basis of the mixture of described lithium source, manganese source and phosphorus source, with respect to 100 weights
The described mixture of amount part, the consumption of described dispersant is 50-500 weight portion, and the consumption of described alloy is 0.01-5.3 weight
Amount part, the consumption of described TiC is 0.1-30 weight portion.
In the step (1) of above-mentioned preparation method, Ti at least meets following condition：Quality purity is 98.5-99.9%, grain
1 μm of ＜ of degree.
In the step (1) of above-mentioned preparation method, the ratio of the amount of the material of Ti and C powder can select in wide scope,
Yield for raising TiC and quality are it is preferable that the ratio of the amount of the material of Ti and C powder is 1：0.8-1.2.
In the step (1) of above-mentioned preparation method, the condition of ball milling can select in wide scope, obtained for improving
Ball milling slurry quality, so that lithium manganese phosphate composite positive pole has excellent chemical property it is preferable that ball milling is at least full
Enough to lower condition：Described mixture, ball milling solvent, the mass ratio of abrading-ball are 1：2-10：3-5；Described ball milling solvent is water, ethanol
One or more of with acetone；The rotating speed of ball milling is 100-400rpm, and the time of ball milling is 2-20h.
In the step (1) of above-mentioned preparation method, the condition of shaping can select in wide scope, but for improving institute
The compactibility of prepared TiC is so that lithium manganese phosphate composite positive pole has excellent cyclical stability it is preferable that the bar of shaping
Part is：Hydrostatic profile under 240-360MPa pressure, and pressurize 3-5min.
In the step (1) of above-mentioned preparation method, the condition of calcining can select in wide scope, but for improving institute
The stability of prepared TiC, thus ensureing the big specific capacitance of lithium manganese phosphate composite positive pole and excellent cyclical stability, excellent
Selection of land, the condition of calcining is：It is warming up to 1800-2400 DEG C from the 18-35 DEG C of heating rate with 2-20 DEG C/min, and in 1800-
2400 DEG C of calcining 1-10h.
In the step (2) of above-mentioned preparation method, the concrete species of lithium source, manganese source, phosphorus source, dispersant and alloy is permissible
Select in wide scope, but the reversible capacity of lithium manganese phosphate composite positive pole and cryogenic property obtained by improving, excellent
Selection of land, lithium source is lithium dihydrogen phosphate, phosphoric acid hydrogen two lithium, lithium hydroxide, lithium acetate, lithium carbonate, tert-butyl alcohol lithium, lithium benzoate, first
Sour lithium, four water citric acid lithiums, lithium phosphate, lithium oxalate, lithium chloride, lithium nitrate, lithium iodide, lithium fluoride, tetrachloro-lithium aluminate, bromination
One or more of lithium, LiBF4 and lithium phosphate；Manganese source is manganese acetate, manganous hydroxide, manganese carbonate, manganese sulfate, dichloro
Change one or more of manganese, manganese oxide；Phosphorus source be phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide,
Sodium dihydrogen phosphate, potassium dihydrogen phosphate and and one or more of lithium dihydrogen phosphate；Dispersant is water, ethanol, in acetone one
Plant or multiple；Alloy be Zr, Zn, Sn, Fe, Ti, Al, Mg, Cu, Cr, Ni, V, Ge, Co, Ag, Au, Mo, Nb, W, La, Ce,
One or more of Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, lanthanum rich rare earth and cerium-rich rare earth compound；
It is highly preferred that lithium source is one or more of lithium dihydrogen phosphate, lithium acetate, lithium carbonate；Manganese source is manganese acetate, carbon
One or more of sour manganese, manganous hydroxide；Phosphorus source is one or more of phosphoric acid, ammonium dihydrogen phosphate；Alloy is oxidation
Iron, silver oxide, magnesia, aluminum oxide, cupric oxide, cerium oxide, zirconium oxide, zinc oxide, ammonium metavanadate, manganese acetate, lanthana, oxygen
Change one or more of neodymium, titanium dioxide, chromic nitrate, magnesium acetate, vanadic anhydride, niobium oxalate, zinc oxide.
In the step (4) of above-mentioned preparation method, the condition of roasting can select in wide scope, from material quality and
Consider it is preferable that roasting at least meets following condition in energy-conserving and environment-protective：The temperature of roasting is 550-1200 DEG C, the time of roasting
For 2-20h.
The lithium manganese phosphate composite positive pole that the present invention provides is to be prepared from by above-mentioned method.
The invention provides application in lithium battery anode for the above-mentioned lithium manganese phosphate composite positive pole.
By technique scheme, the present invention passes through with lithium manganese phosphate as matrix, is coated with TiC and alloy is obtained phosphorus
Sour manganese lithium composite positive pole.The method reaction condition is gentle, process is simple, easy to operate, low production cost, route of synthesis
Simply controlled be easy to the pattern to material and size carries out surrounding and watching regulation and control, be suitable for large-scale production, prepared lithium manganese phosphate is combined
Positive electrode good conductivity, electrical conductivity are high, capacity is high, good rate capability.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of specification, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is X-ray powder diffraction (XRD) figure of the lithium manganese phosphate composite positive pole A1 in detection example 1；
Fig. 2 is SEM (SEM) figure of the lithium manganese phosphate composite positive pole A1 in detection example 2；
Fig. 3 is lithium manganese phosphate composite positive pole A1 in application examples 1 under 2.5-4.4V voltage range, 0.1C multiplying power
Charging and discharging curve figure；
Fig. 4 is lithium manganese phosphate composite positive pole A1 in application examples 1 under 2.5-4.4V voltage range, 1.0C multiplying power
Charging and discharging curve figure.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
Embodiment 1
(1) quality purity is 98.5%, Ti the and C powder of 1 μm of granularity ＜ is with the amount of material than for 1：1 ratio mixing system
Obtain mixture, then with 1：2：3 mass ratio adds water and abrading-ball, with the rotating speed ball milling 2h of 400rpm, be then dried and
Hydrostatic profile under 240MPa pressure, pressurize 5min, then it is warming up to 1800 DEG C from 25 DEG C of heating rates with 2 DEG C/min, and in
1800 DEG C of calcining 10h, cooling, pulverizing are obtained TiC；
(2) by 155.88g lithium dihydrogen phosphate, 367.72g manganese acetate, 3.4g magnesium acetate, 10.1g iron oxide, 0.7g five oxygen
Change two niobiums, 1.0g silver oxide, 20gTiC, be added to dispersed with stirring in 500ml ethanol, then ball milling is to be obtained ball milling slurry；
(3) described ball milling slurry is dried and presoma is obtained, then ball milling, pulverizing, pressed compact are to be obtained base substrate；
(4) described base substrate is placed in nitrogen roasting 16h at 850 DEG C, then cooling, pulverize, jolt ramming to be to be obtained phosphoric acid
Manganese lithium composite positive pole A1.
Embodiment 2
(1) quality purity is 98.5%, Ti the and C powder of 1 μm of granularity ＜ is with the amount of material than for 1：1 ratio mixing system
Obtain mixture, then with 1：2：3 mass ratio adds water and abrading-ball, with the rotating speed ball milling 2h of 400rpm, be then dried and
Hydrostatic profile under 240MPa pressure, pressurize 5min, then it is warming up to 1800 DEG C from 25 DEG C of heating rates with 2 DEG C/min, and in
1800 DEG C of calcining 10h, cooling, pulverizing are obtained TiC；
(2) by 1125.0g lithium acetate, 1150.1g manganese carbonate, 1151.4g ammonium dihydrogen phosphate, 12.8g magnesia, 4.9g oxygen
Change aluminium, 12.8g cupric oxide, 4.8g cerium oxide, 33gTiC, be added to dispersed with stirring in 10L water, then ball milling is to be obtained ball milling slurry
Material；
(3) described ball milling slurry is dried and presoma is obtained, then ball milling, pulverizing, pressed compact are to be obtained base substrate；
(4) described base substrate is placed in argon gas roasting 20h at 550 DEG C, then cooling, pulverize, jolt ramming to be to be obtained phosphoric acid
Manganese lithium composite positive pole A2.
Embodiment 3
(1) quality purity is 98.5%, Ti the and C powder of 1 μm of granularity ＜ is with the amount of material than for 1：1 ratio mixing system
Obtain mixture, then with 1：2：3 mass ratio adds water and abrading-ball, with the rotating speed ball milling 2h of 400rpm, be then dried and
Hydrostatic profile under 240MPa pressure, pressurize 5min, then it is warming up to 1800 DEG C from 25 DEG C of heating rates with 2 DEG C/min, and in
1800 DEG C of calcining 10h, cooling, pulverizing are obtained TiC；
(2) by 38g lithium carbonate, 93.5g manganous hydroxide, 122g85% phosphoric acid dispersed with stirring in 100g water, then plus
1.05g zirconium oxide, 0.6g zinc oxide, 1.5g ammonium metavanadate, 1.8g manganese acetate, 0.35g lanthana and 28gTiC, then ball milling with
Prepared ball milling slurry；
(3) described ball milling slurry is dried and presoma is obtained, then ball milling, pulverizing, pressed compact are to be obtained base substrate；
(4) described base substrate is placed in argon gas roasting 2h at 1200 DEG C, then cooling, pulverize, jolt ramming to be to be obtained phosphoric acid
Manganese lithium composite positive pole A3.
Embodiment 4
(1) quality purity is 98.5%, Ti the and C powder of 1 μm of granularity ＜ is with the amount of material than for 1：1 ratio mixing system
Obtain mixture, then with 1：2：3 mass ratio adds water and abrading-ball, with the rotating speed ball milling 2h of 400rpm, be then dried and
Hydrostatic profile under 240MPa pressure, pressurize 5min, then it is warming up to 1800 DEG C from 25 DEG C of heating rates with 2 DEG C/min, and in
1800 DEG C of calcining 10h, cooling, pulverizing are obtained TiC；
(2) by 107.0g lithium acetate, 114.5g manganese carbonate, 115.2g ammonium dihydrogen phosphate dispersed with stirring in 200ml volume ratio
In the mixed solution of second alcohol and water for 1: 1, add 5.3g iron oxide, 0.2g neodymia, 0.2g titanium dioxide, 0.25g nitre
Sour chromium and 3.2gTiC, then ball milling is to be obtained ball milling slurry；
(3) described ball milling slurry is dried and presoma is obtained, then ball milling, pulverizing, pressed compact are to be obtained base substrate；
(4) described base substrate is placed in nitrogen roasting 10h at 900 DEG C, then cooling, pulverize, jolt ramming to be to be obtained phosphoric acid
Manganese lithium composite positive pole A4.
Embodiment 5
(1) quality purity is 98.5%, Ti the and C powder of 1 μm of granularity ＜ is with the amount of material than for 1：1 ratio mixing system
Obtain mixture, then with 1：2：3 mass ratio adds water and abrading-ball, with the rotating speed ball milling 2h of 400rpm, be then dried and
Hydrostatic profile under 240MPa pressure, pressurize 5min, then it is warming up to 1800 DEG C from 25 DEG C of heating rates with 2 DEG C/min, and in
1800 DEG C of calcining 10h, cooling, pulverizing are obtained TiC；
(2) by 156.0g lithium dihydrogen phosphate, 173.80g manganese carbonate, 3.4g magnesium acetate, 5.0g vanadic anhydride, 0.35g grass
Sour niobium, 0.18g zinc oxide and 30gTiC, are added to dispersed with stirring in 500ml ethanol, and then ball milling is to be obtained ball milling slurry；
(3) described ball milling slurry is dried and presoma is obtained, then ball milling, pulverizing, pressed compact are to be obtained base substrate；
(4) described base substrate is placed in nitrogen roasting 16h at 650 DEG C, then cooling, pulverize, jolt ramming to be to be obtained phosphoric acid
Manganese lithium composite positive pole A5.
Detection example 1
With the X-ray powder diffraction instrument of Japanese Shimadzu Corporation XRD-7000S model to lithium manganese phosphate composite positive pole A1
Carry out Discriminating materials, result is shown in Fig. 1, compare with the standard card of lithium manganese phosphate and understand, characteristic peak is obvious, and no miscellaneous peak occurs,
The lithium manganese phosphate composite positive pole A1 that surface is obtained is purity and the higher lithium manganese phosphate of degree of crystallinity.
In the same manner A2-A5 is detected, testing result is consistent substantially with the XRD of A1.
Detection example 2
With the JSM-6700F SEM of Japanese electricity company, shape is carried out to lithium manganese phosphate composite positive pole A1
Looks are analyzed, and result is shown in Fig. 2.
In the same manner A2-A5 is detected, testing result is consistent substantially with the SEM figure of A1.
Detection example 3
With the 9300Z laser particle size analyzer of Dandong Bai Te Instrument Ltd. to obtained manganese phosphate in embodiment 1
Lithium composite positive pole A1 is analyzed, and records D50 and is 11.42 μm.
In the same manner A2-A5 is detected, testing result is consistent substantially with A1.
Detection example 4
With U.S. health tower NOVA 4000e, obtained lithium manganese phosphate composite positive pole A1 in embodiment 1 is carried out comparing table
The mensure of area, recording specific surface area is 24.534m2/g.
In the same manner A2-A5 is detected, testing result is consistent substantially with A1.
Detection example 5
With the Autotap of U.S. Kang Ta, jolt ramming is carried out to obtained lithium manganese phosphate composite positive pole A1 in embodiment 1
The mensure of density, recording tap density is 1.43g/cm3.
In the same manner A2-A5 is detected, testing result is consistent substantially with A1.
Application examples 1
By the lithium manganese phosphate composite positive pole being obtained in embodiment 1 and adhesive polyvinylidene fluoride PVDF and conduction
Carbon black presses 92: 5: 3 weight than ground and mixed, and adds 1-METHYLPYRROLIDONE NMP to be tuned into slurry as dispersant, uniformly applies
Overlay on Al paper tinsel, tabletted prepared lithium manganese phosphate anode composite after 110 DEG C of dryings 12 hours.Then in high-purity argon gas protection
In German Braun MBRAUN glove box, the lithium manganese phosphate anode composite being obtained and battery cathode sheet are assembled into button cell.
Wherein, negative pole is metal lithium sheet；Electrolyte is the volume ratio containing 1mol/L LiPF6 is EC:DMC:EMC=1:1:1 mixing is molten
Liquid；Barrier film is Celgard2400 microporous barrier.
By the button battery of assembling under the voltage range of 2.5-4.4V, enter under the conditions of 0.1C and 1.0C multiplying power respectively
Row constant current charge-discharge test, test result is：Under 0.1C multiplying power, the first discharge specific capacity of battery reaches 141.8mAh/g,
Initial coulomb efficiency is 95.7%；In 1.0C rate charge-discharge, the discharge capacity of material is 122.4mAh/g, coulomb effect first
Rate is 97.6% for capability retention after 78.5%, and 100 charge and discharge cycles.Fig. 3 is lithium manganese phosphate composite positive pole A1
Charging and discharging curve figure under 2.5-4.4V voltage range, 0.1C multiplying power；Fig. 4 is lithium manganese phosphate composite positive pole A1 in 2.5-
Charging and discharging curve figure under 4.4V voltage range, 1.0C multiplying power.Prepared lithium manganese phosphate anode composite be can be seen that from figure
Material cycle performance very excellent.
In the same manner A2-A4 is detected, testing result is consistent substantially with the testing result of A1.
Data above shows the good conductivity of lithium manganese phosphate composite positive pole disclosed by the invention, electrical conductivity height, capacity
High, good rate capability.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The combination of energy no longer separately illustrates.
Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of lithium manganese phosphate composite positive pole is it is characterised in that described preparation method includes：
(1) Ti and C powder is mixed to prepare mixture, then ball milling, drying, shaping, calcining, cooling, pulverizing is obtained TiC；
(2) lithium source, manganese source, phosphorus source are added dispersed with stirring in dispersant, be subsequently added into alloy and described TiC carry out ball milling with
Prepared ball milling slurry；
(3) described ball milling slurry is dried and presoma is obtained, then ball milling, pulverizing, pressed compact are to be obtained base substrate；
(4) described base substrate is placed in inert gas and carries out roasting, cooling, pulverizing, jolt ramming so that lithium manganese phosphate anode composite is obtained
Material；
Wherein, elemental lithium in described lithium source, manganese element in described manganese source, the ratio of the amount of material of P elements is in phosphorus source
0.85-1.25：0.9-1.1：0.98-1.02；On the basis of the mixture of described lithium source, manganese source and phosphorus source, with respect to 100 weight
The described mixture of part, the consumption of described dispersant is 50-500 weight portion, and the consumption of described alloy is 0.01-5.3 weight
Part, the consumption of described TiC is 0.1-30 weight portion.
2. preparation method according to claim 1, wherein, in step (1), described Ti at least meets following condition：Matter
Amount purity is 98.5-99.9%, 1 μm of granularity ＜.
3. preparation method according to claim 1 and 2, wherein, in step (1), the amount of material of described Ti and C powder
Than for 1：0.8-1.2.
4. the preparation method according to claim 1 or 3, wherein, in step (1), described ball milling at least meets following bar
Part：Described mixture, ball milling solvent, the mass ratio of abrading-ball are 1：2-10：3-5；Described ball milling solvent is in water, ethanol and acetone
One or more；The rotating speed of ball milling is 100-400rpm, and the time of ball milling is 2-20h.
5. preparation method according to claim 3, wherein, in step (1), the condition of described shaping is：In 240-
Hydrostatic profile under 360MPa pressure, and pressurize 3-5min.
6. preparation method according to claim 1 or 5, wherein, in step (1), the condition of described calcining is：From 18-
35 DEG C of heating rates with 2-20 DEG C/min are warming up to 1800-2400 DEG C, and calcine 1-10h in 1800-2400 DEG C.
7. the preparation method according to claim 1-6 any one, wherein, in step (2), described lithium source is di(2-ethylhexyl)phosphate
Hydrogen lithium, phosphoric acid hydrogen two lithium, lithium hydroxide, lithium acetate, lithium carbonate, tert-butyl alcohol lithium, lithium benzoate, lithium formate, four water citric acid lithiums,
Lithium phosphate, lithium oxalate, lithium chloride, lithium nitrate, lithium iodide, lithium fluoride, tetrachloro-lithium aluminate, lithium bromide, LiBF4 and phosphoric acid
One or more of lithium；
Described manganese source is one or more of manganese acetate, manganous hydroxide, manganese carbonate, manganese sulfate, manganous chloride, manganese oxide；
Phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide, sodium dihydrogen phosphate, di(2-ethylhexyl)phosphate
Hydrogen potassium and and one or more of lithium dihydrogen phosphate；
Described dispersant is one or more of water, ethanol, acetone；
Described alloy be Zr, Zn, Sn, Fe, Ti, Al, Mg, Cu, Cr, Ni, V, Ge, Co, Ag, Au, Mo, Nb, W, La, Ce, Pr,
One or more of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, lanthanum rich rare earth and cerium-rich rare earth compound；
Preferably, described lithium source is one or more of lithium dihydrogen phosphate, lithium acetate, lithium carbonate；Described manganese source be manganese acetate,
One or more of manganese carbonate, manganous hydroxide；Phosphorus source is one or more of phosphoric acid, ammonium dihydrogen phosphate；Described mix
Debris are iron oxide, silver oxide, magnesia, aluminum oxide, cupric oxide, cerium oxide, zirconium oxide, zinc oxide, ammonium metavanadate, acetic acid
One of manganese, lanthana, neodymia, titanium dioxide, chromic nitrate, magnesium acetate, vanadic anhydride, niobium oxalate, zinc oxide or many
Kind.
8. preparation method according to claim 3, wherein, in step (4), described roasting at least meets following condition：
The temperature of roasting is 550-1200 DEG C, and the time of roasting is 2-20h.
9. a kind of lithium manganese phosphate composite positive pole is it is characterised in that described lithium manganese phosphate composite positive pole will by right
The preparation method described in any one in 1-8 is asked to be prepared from.
10. application in lithium ion cell positive for a kind of lithium manganese phosphate composite positive pole according to claim 9.
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| CN108400330A (en) * | 2018-03-08 | 2018-08-14 | 蒋央芳 | A kind of preparation method of carbon doping phosphoric acid manganese (III) |
| CN114220969A (en) * | 2021-12-08 | 2022-03-22 | 山东昭文新能源科技有限公司 | Preparation method of lithium titanium silicate |
| WO2023123979A1 (en) * | 2022-06-30 | 2023-07-06 | 北京当升材料科技股份有限公司 | Olivine composite positive-electrode material, preparation method and application thereof, and lithium-ion battery |
| CN117246990A (en) * | 2023-11-16 | 2023-12-19 | 合肥国轩高科动力能源有限公司 | Lithium iron manganese phosphate, preparation method thereof and lithium ion battery |
| CN118651838A (en) * | 2024-08-21 | 2024-09-17 | 四川大学 | Modification method of lithium iron manganese phosphate |
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| CN108400330A (en) * | 2018-03-08 | 2018-08-14 | 蒋央芳 | A kind of preparation method of carbon doping phosphoric acid manganese (III) |
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