CN106159202A - Originally seek peace metal doping nano porous chips lithium manganese phosphate material, its preparation method and application - Google Patents
Originally seek peace metal doping nano porous chips lithium manganese phosphate material, its preparation method and application Download PDFInfo
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- CN106159202A CN106159202A CN201510125580.1A CN201510125580A CN106159202A CN 106159202 A CN106159202 A CN 106159202A CN 201510125580 A CN201510125580 A CN 201510125580A CN 106159202 A CN106159202 A CN 106159202A
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Abstract
The invention discloses one originally to seek peace metal doping nano porous chips lithium manganese phosphate material, it comprises by the nanocrystalline nanometer sheet constituted that particle diameter is 20～50nm, the gap having width to be 10～40nm between the most nanocrystalline, and the thickness of described nanometer sheet is less than 100nm, length and/or width are 1～10 μm, and the chemical formula of described lithium manganese phosphate material is LiMnxMzPO4, wherein 0 < x≤1,0.001 < z < 1, x+z=1, M is bivalent metal ion.The invention also discloses the preparation method and application of described nanoporous sheet lithium manganese phosphate material.The nanoporous sheet lithium manganese phosphate material of the present invention has excellent electric property, and preparation process is simple and easy to control, energy-conserving and environment-protective, is suitable to large-scale production.
Description
Technical field
The present invention relates to a kind of lithium manganese phosphate material, to have originally seeking peace of potential high-energy-density density metal-doped particularly to a kind of
Nanoporous sheet lithium manganese phosphate material and its preparation method and application, belongs to Inorganic Non-metallic Materials, energy-storage battery Material Field.
Background technology
Lithium ion battery is the green energy-storing system received much attention in recent years, its have lightweight, energy storage is big, power is high, safety
The advantages such as performance is good, life-span length, self discharge coefficient are little, it has also become various portable type electronic products and the head of communication tool storage source
Choosing, and progressively it is developed to the electrical source of power of electric automobile, thus promote it to safer, environmental protection, low cost and high-energy-density
Direction develop.Goodenough in 1997 et al. reports olivine structural LiMPO4(M=Fe, Mn, Co's etc.)
After storage lithium characteristic, this type of material is with its specific capacity height, Stability Analysis of Structures, Heat stability is good, and safety advantages of higher becomes lithium
One of emphasis that electricity positive electrode is paid close attention to.But its development of the ionic conductance that this type of material is low and electronic conductance yoke always.At present
LiFeO4Have been commercialized, use carbon coating technology and reduce particle size raising material electronics conductance and ionic conductance, making material energy
Enough give play to the 80～90% of its theoretical capacity (171mAh/g).But LiFePO4Voltage low (3.4V vs.Li), specific energy
Density (theoretical 578Wh/kg) is the highest, it is impossible to meet the requirement of high-performance electrical source of power.In recent years, the research of this type of material
Emphasis has transferred to LiMnPO4.It practice, LiMnPO4Voltage platform be 4.1V (vs.Li), LiFePO to be compared4Height,
In addition with LiFePO4Suitable theoretical capacity 170mAh/g, its theoretical specific energy density 700Wh/kg LiFeO to be compared4High by 20%
Many.But LiMnPO4Electronic conductance and ionic conductance all far below LiFePO4, material is processed and the requirement of preparation method
LiFePO to be compared4Much higher, so LiMnPO4Progress the slowest.Improve LiMnPO at present4Electronic conductance
Method mainly has particle surface carbon to be coated with, ion doping, prepares part Fe substituted solid solution LiMn1-xFexPO4, and once
Granule nanorize.Wherein, primary particle nanorize can shorten electronics and Li+At LiMnPO4The transmission range of body phase, can be simultaneously
Improve electronic conductance and ionic conductance.Make a general survey of document it can be seen that sufficiently carbon cladding and nano-particle have been LiMnPO4Play
The essential condition of its high-energy-density.LiMnPO4The main path of nanorize can substantially divide two classes: 1) with solvent-thermal method, sol-gel,
The elegant synthetic methods preparation nano-particle purely such as spray pyrolysis；2) with spherical precursor MnPO4·H2Based on O, preparation
Porous micro-nanosphere structure.It is known that it is unreal that fine synthetic method is applied to electrode material production process
Border, and nano-particle tap density purely is low, and specific volume energy density is low, is not also suitable for electrical source of power.For micro-
The porous micro-nanosphere LiMnPO of nano compound structure4, relatively though the former simply, obtains material tap density to preparation method
The highest, but it is reported, due to its isotropic micron-scale, carbon source and electrolyte to granule diffusion inside path length, and
And diffusion process is easily limited by duct and is easily obstructed, so the carbon cladding of a nano-particle within micron particle and electrolyte
Infiltration always can not be relatively abundant, thus affects the performance of material overall performance.Therefore exploiting economy, synthetic method simple and easy to control,
Preparation is applicable to the LiMnPO of the high-energy-density density of electrical source of power4Still suffer from much challenging.
Summary of the invention
In view of the deficiencies in the prior art, offer is provided and a kind of there is originally seeking peace of potential high-energy-density density
Metal doping nano porous chips lithium manganese phosphate material.
A further object of the present invention is to provide a kind of in order to prepare described metal doping nano porous chips lithium manganese phosphate material of seeking peace
Material, and method simple and easy to control.
It is still another object of the present invention to provide the purposes of described metal doping nano porous chips lithium manganese phosphate material of seeking peace.
For realizing aforementioned invention purpose, the technical solution used in the present invention includes:
One is originally sought peace metal doping nano porous chips lithium manganese phosphate material, and it comprises by particle diameter is 20～50nm nanocrystalline constitute
Nanometer sheet, the most nanocrystalline between have width to be 10～40nm gap, and the thickness of described nanometer sheet is less than 100nm,
Length and/or width are 1～10 μm.
Further, the chemical formula of described lithium manganese phosphate material is LiMnxMzPO4, wherein 0 < x≤1,0.001 < z < 1,
(x+z)=1, M are bivalent metal ion.
Wherein, M includes Fe2+, Co2+, Ni2+, Mg2+, Zn2+, Cu2+In the combination of any one or more, but not
It is limited to this.
The preparation method of described metal doping nano porous chips lithium manganese phosphate material of seeking peace includes:
(1) taking phosphoric acid to add in Mn salt and metal M dopant source solution, making (Mn+M) is 1 with the mol ratio of P:
1.05～1.1, after mix homogeneously, add organic amine, the pH value to reaction system is 8～10 (preferably 8-9), continues stirring
More than 1h, isolates solid content therein and washs, after drying, it is thus achieved that presoma；
(2) Mn:P:Li=1:1:1.0～1.1 in molar ratio, uniformly mixes described presoma with lithium salts in organic solvent,
Obtain precursor-lithium salts suspension, afterwards suspension is dried, it is thus achieved that presoma-lithium salt mixture；
(3) described presoma-lithium salt mixture is calcined under the temperature conditions higher than described lithium salts fusing point more than 5h, it is thus achieved that institute
State lithium manganese phosphate material.
As one of preferred embodiment, step (1) including: takes bivalence Mn salt and dissolves in a solvent, is made into manganese ion concentration
It is the manganese salt solution of 0.1～2mol/L, then takes the phosphoric acid described manganese salt solution of addition mix homogeneously, afterwards organic amine is added reaction
In system, until pH value=8 of reaction system～9, after being further continued for stirring at least 1h, isolate solid content therein and wash
After, it is dried 2～5h at 80～120 DEG C, it is thus achieved that described presoma.
Further, described solvent includes ethanol or water, but is not limited to this.
Further, described manganous salt is at least selected from manganese sulfate, manganese nitrate, protochloride manganese, manganese acetate, and is not limited to this.
As one of preferred embodiment, step (1) also includes: by bivalence Mn salt and the metal M doping of stoichiometric proportion
Agent source is dissolved and is formed homogeneous solution in a solvent, adds the phosphoric acid of corresponding mol ratio, after mix homogeneously, adds organic amine to instead
Answer pH value=8～10 of system, after continuing to stir at least 1h, isolate solid content therein and wash dry, it is thus achieved that before described
Drive body.
Further, if Fe2+Doping, then at least should be at N in step (1)2Or complete under argon hydrogen protective atmosphere described uniformly
The preparation of solution, phosphoric acid, the interpolation of organic amine, and reaction generate the operation of described solid content,
Further, described organic amine is at least selected from ethylenediamine, 1,3-propane diamine, Putriscine, and is not limited to this.
Further, the chemical formula of described presoma includes (C2N2H10)(MnxMz)2(PO4)2·yH2O, (C3N2H12)(MnxMz)2
(PO4)2·yH2O, (C4N2H14)(MnxMz)2(PO4)2·yH2O, wherein 0 < x≤1,0.001 < z < 1, (x+z)=1,0≤y
< 10, M is bivalent metal ion.
Wherein, the chemical composition of nano thickness thin slice presoma (the most described presoma, or title nanometer sheet presoma) is according to used
Organic amine and the difference of metal dopant and different.
Further, described divalent metal doped source is soluble-salt, and described soluble-salt includes Co2+, Ni2+, Mg2+, Zn2+,
Cu2+Sulfate, acetate, nitrate, chloride and ferrous sulfate in the combination of any one or more, and not
It is limited to this.
As one of preferred embodiment, step (2) including: takes lithium salts dissolving and forms lithium salt solution in ethanol, then by described
Presoma adds described lithium salt solution, uniformly after mixing also ultrasonic disperse, it is thus achieved that homodisperse precursor-lithium salts suspension, and will
Described precursor-lithium salts suspension at 100 DEG C, 0.1～0.5h flash baking, it is thus achieved that presoma-lithium salt mixture.
Further, described lithium salts is at least selected from lithium nitrate, lithium acetate, lithium chloride, Lithium hydrate, and is not limited to this.
As one of preferred embodiment, step (3) including: under chosen atmosphere, is existed by described presoma-lithium salt mixture
200～400 DEG C of calcinings 5～10h, it is thus achieved that described lithium manganese phosphate material, wherein said chosen atmosphere is at least selected from air, nitrogen, argon
Any one in hydrogen gaseous mixture atmosphere.
Further, if described presoma is Fe2+Doping, then in step (3), calcination process should be at N2Or argon hydrogen protective atmosphere
Under carry out.
The lithium manganese phosphate material of a kind of carbon cladding, it comprises: described metal doping nano porous chips lithium manganese phosphate material of seeking peace；
And, it is coated with the carbon-coating of described nanoporous sheet lithium manganese phosphate material.
Further, the lithium manganese phosphate material of described carbon cladding comprises the carbon and described lithium manganese phosphate material that mass ratio is 0.5～10%:1
Material.
Further, the tap density of the lithium manganese phosphate material of described carbon cladding is 0.9～2g/cm3, 0.1C specific discharge capacity is
140mAh·g-1Above.
The preparation method of the lithium manganese phosphate material of described carbon cladding includes:
Take described metal doping nano porous chips lithium manganese phosphate material of seeking peace be dispersed in solvent with carbon source and be sufficiently mixed,
Forming the dispersion liquid of lithium manganese phosphate-carbon source, wherein carbon source with the mass ratio of described nanoporous sheet lithium manganese phosphate material is
10%～30%:1；
By the dispersion liquid of described lithium manganese phosphate-carbon source at 100～120 DEG C, after 0.1～1h flash baking, at N2Or argon hydrogen gaseous mixture
Under atmosphere, 600～650 DEG C of heat treatments 3～5h, it is thus achieved that the lithium manganese phosphate material of described carbon cladding.
Further, described carbon source is at least selected from glucose, sucrose, fructose, soluble starch, Polyethylene Glycol, but is not limited to
This.
Further, described solvent includes water or ethanol, but is not limited to this.
A kind of energy storage device, it comprises described seek peace metal doping nano porous chips lithium manganese phosphate material or the phosphorus of described carbon cladding
Acid manganese lithium material.
Than prior art, the invention have the advantages that
(1) the metal doping nano porous chips lithium manganese phosphate material of originally seeking peace of the present invention (is called for short " nanoporous sheet manganese phosphate lithio
Material "), wherein form nanocrystalline only the 20～50nm of nanometer sheet, particle size is little, electronics and Li+Expand mutually at lithium manganese phosphate body
Dissipate apart from short, improve electronics and the ionic conductance of material simultaneously.And, it is higher that micron order chip size ensure that material has
Tap density.Meanwhile, the high porosity of sheet and nano thickness make this type of material than the multi-pore micron ball particle in document, carbon
Source is prone to diffuse to internal particle, and metal-doped lithium manganese phosphate of originally seeking peace is nanocrystalline to be easily coated with by sufficient carbon, thus easily realizes
Sufficiently carbon cladding, improves material electronics conductance, and in the battery, the hole that electrolyte is also easy to from thickness direction diffuses to inside
Granule, fully infiltrates internal particle.Tiny is nanocrystalline, and the sheet of nano thickness and loose structure, make material have latent in addition
In high-energy-density density.Especially after material carbon is coated with, electrical property is excellent, and tap density is 0.9～2g/cm3, and in document
The tap density of the multi-pore micron ball of report is suitable, than the tap density (0.3～0.6g/cm of the nano-particle of report in document3)
Much higher.
(2) preparation method of the nanoporous sheet lithium manganese phosphate of the present invention, be utilize organic amine phosphate nanometer sheet for presoma,
Only the nanoporous sheet phosphorus of good crystallinity need to be i.e. can get by the calcining heat heat treatment between 200～400 DEG C after mixing with lithium salts
Acid manganese lithium, than the general raw material solid phase synthesis calcining heat 600 of lithium manganese phosphate～700 DEG C low, thus energy resource consumption reduces.Have
Machine amine phosphate nanometer sheet is obtained by simple solution chemical processes, and productivity can be not required to adjuvant and special installation close to 100%,
Easily accomplish scale production.
(3) the nanoporous sheet lithium manganese phosphate of the present invention, its forerunner's system uses coprecipitation method to obtain, and relatively conventional solid spreads
Doping method, evenly, doping effect is more preferable in doping.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of embodiment 1 obtained nanometer sheet presoma；
Fig. 2 is energy dispersion X-ray (EDAX) collection of illustrative plates of embodiment 1 obtained nanometer sheet presoma；
Fig. 3 is embodiment 1 obtained nanoporous sheet LiMnPO4Scanning electron microscope (SEM) photo；
Fig. 4 is embodiment 1 obtained nanoporous sheet LiMnPO4Scanning electron microscope (SEM) photo after carbon cladding；
Fig. 5 is embodiment 1 obtained nanoporous sheet LiMnPO4Discharge and recharge discharge curve after carbon is coated with.
Detailed description of the invention
Below in conjunction with some embodiments, technical scheme is further illustrated.
Embodiment 1
1) by 0.02mol MnSO4·H2O is dissolved in 100mL deionized water, by 1.5ml (about 0.022mol H3PO4)
Strong phosphoric acid (mass fraction > 85%), instill MnSO with syringe4After solution, stir 20 minutes, speed of agitator 200r/min.
With syringe, ethylenediamine is slowly dropped in (about 0.005ml/s) reaction system, in real time monitoring reaction system PH, until PH=8.5,
Stop dropping, continue stirring 1h.Lightpink precipitation being filtered and is washed with deionized 3 times, 100 DEG C are dried 6h and obtain 3.88g
(C2N2H10)Mn2(PO4)2.2H2O nanometer sheet presoma (productivity 97.5% does not include the insubstantial loss during filtration washing).
2) by step 1) in the 3.88g (C that obtains2N2H10)Mn2(PO4)2.2H2O nanometer sheet presoma joins 40ml and dissolves
Have in the ethanol solution of 1.38g (0.02mol) lithium nitrate, stirring, ultrasonic after obtain homodisperse precursor-lithium salts suspension.
Then suspension is placed in flash baking in the baking oven of 80 DEG C.
3) the mixed uniformly precursor-lithium salts after drying is placed in Muffle furnace, in atmosphere 350 DEG C of insulation 10h, after cooling
I.e. obtain nanoporous sheet LiMnPO4。
4) by step 3) the nanoporous sheet LiMnPO that obtains4The 30% of quality weighs glucose, by LiMnPO4And Fructus Vitis viniferae
Sugar ultrasonic disperse 1h in 30mL ethanol, obtains uniform suspension, then by suspension 100 DEG C, 10min flash baking.
N2Under atmosphere, by 650 DEG C of high-temperature process 3h of dry powder, after cooling, obtain the material LiMnPO4-C of carbon cladding.
Refering to Fig. 1, the presoma (C that this embodiment obtains2N2H10)Mn2(PO4)2.2H2O nanometer sheet thickness is about 50nm, width
For micron order.Refering to Fig. 3, the LiMnPO4 nanometer sheet that this presoma nanometer sheet changes into has good loose structure, sheet by
The nano-particle composition of about 30nm, has the gap of about 20nm between granule.After this nanoporous sheet LiMnPO4 carbon cladding,
Still keep fine porous chips structure (as shown in Figure 4).After tested, the phosphorus content of carbon encapsulated material is 7.6%, vibration density
Degree is 1.1g cm-3.LiMnPO4-C material list after carbon cladding reveals excellent electrical property, and refering to Fig. 5, its 0.01C discharges
Capacity is up to 158mAh g-1If removing its phosphorus content, this capacity is close to theoretical capacity (the 170mAh g of material-1), 0.1C holds
Amount 146mAh g-1, this is that the technology that existing same type document is reported is unapproachable.
Embodiment 2
1) by 0.02mol MnCl2·4H2O is dissolved in 100mL ethanol, by 1.5ml (about 0.022mol H3PO4) dense phosphorus
Acid (mass fraction > 85%), instill MnCl with syringe2After solution, stir 20 minutes, speed of agitator 200r/min.With note
Emitter is by 1, and 3-propane diamine is slowly dropped in (about 0.005ml/s) reaction system, in real time monitoring reaction system PH, until PH=8.5,
Stop dropping, continue stirring 1h.Lightpink precipitation being filtered and is washed with deionized 3 times, 100 DEG C are dried 6h and obtain 4.05g
(C3N2H12)Mn2(PO4)2.2H2O nanometer sheet (productivity 98.3% does not include the insubstantial loss during filtration washing).
2) by step 1) in the 4.05g (C that obtains3N2H12)Mn2(PO4)2.2H2O nanometer sheet joins 40ml and is dissolved with 2.04
In the ethanol solution of g (0.02mol) Lithium acetate dihydrate, stirring, ultrasonic after obtain homodisperse precursor-lithium salts suspension.So
After by suspension flash baking.
3) the mixed uniformly precursor-lithium salts after drying is placed in tube furnace, at N2380 DEG C of insulation 10h, fall in atmosphere
Nanoporous sheet LiMnPO is i.e. obtained after temperature4。
4) by step 3) the nanoporous sheet LiMnPO that obtains4The 30% of quality weighs sucrose, by LiMnPO4Exist with sucrose
Ultrasonic disperse 1h in 30mL ethanol, obtains uniform suspension, then by suspension 100 DEG C, 10min flash baking.N2Gas
Under atmosphere, by 650 DEG C of high-temperature process 3h of dry powder, after cooling, obtain the material LiMnPO of carbon cladding4-C。
The nanoporous sheet LiMnPO that the present embodiment obtains4Thickness about 80nm, sheet is made up of the nano-particle of 30～50nm,
The gap of 20～40nm, material LiMnPO after carbon cladding is had between granule4The carbon content of-C is 7.8%, tap density 1.3g cm-3,
0.1C discharge capacity is 141mAh g-1。
Embodiment 3
1)N2Under atmosphere, by 0.014mol MnCl2.4H2O and 0.006mol FeSO4.7H2O is dissolved in 100mL deionization
In water, by 1.5ml (about 0.022mol H3PO4) strong phosphoric acid (mass fraction > 85%), instill MnCl with syringe2And FeSO4
After mixed solution, stir 20 minutes, speed of agitator 200r/min.Ethylenediamine is slowly dropped into (about 0.005ml/s) with syringe
In reaction system, monitoring reaction system PH in real time, until PH=8.5, stop dropping, continue stirring 1h.Precipitation is filtered also
Being washed with deionized 3 times, 70 DEG C are dried 6h and obtain 3.9g (C2N2H10)(Mn0.7Fe0.3)2(PO4)2.2H2O nanometer sheet (productivity
98.2%, do not include the insubstantial loss during filtration washing).
2) by step 1) in the 3.9g (C that obtains2N2H10)(Mn0.7Fe0.3)2(PO4)2.2H2O nanometer sheet joins 40ml and dissolves
Have in the ethanol solution of 2.04g (0.02mol) Lithium acetate dihydrate, stirring, ultrasonic after to obtain homodisperse precursor-lithium salts suspended
Liquid.Then by suspension flash baking.
3) the mixed uniformly precursor-lithium salts after drying is placed in tube furnace, at N2In 350 DEG C insulation 10h, after cooling
I.e. obtain nanoporous sheet Li Mn0.7Fe0.3PO4。
4) by step 3) the nanoporous sheet Li Mn that obtains0.7Fe0.3PO4The 30% of quality weighs PEG-400, by LiMnPO4
With PEG-400 ultrasonic disperse 1h in 30mL ethanol, obtaining uniform suspension, then by suspension 100 DEG C, 10min is fast
Speed is dried.N2Under atmosphere, by 650 DEG C of high-temperature process 3h of dry powder, after cooling, obtain the material Li Mn of carbon cladding0.7Fe0.3PO4-C。
The nanoporous sheet Li Mn that the present embodiment obtains0.7Fe0.3PO4-C thickness about 80nm, sheet by 40～50nm nano-particle
Composition, has between granule～the gap of 20nm, material Li Mn after carbon cladding0.7Fe0.3PO4The carbon content of-C is 3.01%, jolt ramming
Density 1.5g cm-3, 0.1C discharge capacity is 156mAh g-1。
It should be noted that in this article, term " includes ", " comprising " or its any other variant are intended to nonexcludability
Comprise so that include that the process of a series of key element, method, article or equipment not only include those key elements, but also
Including other key elements being not expressly set out, or also include want intrinsic for this process, method, article or equipment
Element.
The above is only the detailed description of the invention of the present invention, it is clear that described embodiment is only that a part of the present invention is implemented
Example rather than whole embodiments.It should be pointed out that, for those skilled in the art, without departing from this
Can also make some improvements and modifications on the premise of bright principle, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (12)
1. a metal doping nano porous chips lithium manganese phosphate material of originally seeking peace, it is characterised in that described lithium manganese phosphate sill comprises
By the nanocrystalline nanometer sheet constituted that particle diameter is 20～50nm, the most nanocrystalline between have width to be 10～40nm gap, and
The thickness of described nanometer sheet is less than 100nm, and length and/or width are 1～10 μm；
The chemical formula of described lithium manganese phosphate sill is LiMnxMzPO4, wherein 0 < x≤1,0.001 < z < 1, (x+z)=1,
M is bivalent metal ion, and described bivalent metal ion includes Fe2+, Co2+, Ni2+, Mg2+, Zn2+, Cu2+In any one
Or two or more combinations.
2. the preparation method of metal doping nano porous chips lithium manganese phosphate material of originally seeking peace as claimed in claim 1, it is characterised in that including:
(1) taking phosphoric acid to add in Mn salt and metal M dopant source solution, making (Mn+M) is 1 with the mol ratio of P:
1.05～1.1, after mix homogeneously, add organic amine, the pH value to reaction system is 8～10, continues stirring more than 1h, separates
Go out solid content therein and wash, after drying, it is thus achieved that presoma；
(2) (Mn+M): P:Li=1:1:1.0～1.1 in molar ratio, by described presoma and lithium salts in organic solvent all
Even mixing, it is thus achieved that precursor-lithium salts suspension, is dried suspension, it is thus achieved that presoma-lithium salt mixture afterwards；
(3) described presoma-lithium salt mixture is calcined under the temperature conditions higher than described lithium salts fusing point more than 5h, it is thus achieved that institute
State lithium manganese phosphate material.
The preparation method of metal doping nano porous chips lithium manganese phosphate material of the most originally seeking peace, it is characterised in that step
Suddenly (1) including: taking bivalence Mn salt and metal M dopant source dissolves in a solvent, being made into manganese ion concentration is 0.1～2mol/L
Solution, then take phosphoric acid and add above-mentioned solution mix homogeneously, afterwards organic amine is added in reaction system, until reaction system
PH value=8～10, after being further continued for stirring at least 1h, isolate solid content therein and wash after, 50～120 DEG C be dried
2～10h, it is thus achieved that described presoma；
Wherein, described solvent includes ethanol or water, and described manganous salt is at least selected from manganese sulfate, manganese nitrate, protochloride manganese, vinegar
Acid manganese；
Described metal M dopant source is at least selected from Co2+, Ni2+, Mg2+, Zn2+, Cu2+Sulfate, acetate, nitrate,
Chloride and ferrous sulfate.
4. according to the preparation method of metal doping nano porous chips lithium manganese phosphate material of originally seeking peace according to any one of claim 2-3, its
It is characterised by that described organic amine is at least selected from ethylenediamine, 1,3-propane diamine, Putriscine.
5. according to the preparation method of metal doping nano porous chips lithium manganese phosphate material of originally seeking peace according to any one of claim 2-3, its
It is characterised by that the chemical formula of described presoma includes (C2N2H10)(MnxMz)2(PO4)2·yH2O, (C3N2H12)(MnxMz)2
(PO4)2·yH2O, (C4N2H14)(MnxMz)2(PO4)2·yH2O, wherein 0 < x≤1,0.001 < z < 1, (x+z)=1,0≤y
< 10, M is bivalent metal ion.
The preparation method of metal doping nano porous chips lithium manganese phosphate material of the most originally seeking peace, it is characterised in that step
Suddenly (2) including: takes lithium salts dissolving and forms lithium salt solution in ethanol, more described presoma adds described lithium salt solution, uniformly
After mixing ultrasonic disperse, it is thus achieved that homodisperse precursor-lithium salts suspension, by described precursor-lithium salts suspension at 100 DEG C,
0.1～0.5h flash baking, it is thus achieved that presoma-lithium salt mixture.
7., according to the preparation method of metal doping nano porous chips lithium manganese phosphate material of originally seeking peace described in Claims 2 or 3, its feature exists
In described lithium salts at least selected from lithium nitrate, lithium acetate, lithium chloride, Lithium hydrate.
The preparation method of metal doping nano porous chips lithium manganese phosphate material of the most originally seeking peace, it is characterised in that step
Suddenly (3) including: under chosen atmosphere, at 200～400 DEG C, described presoma-lithium salt mixture is calcined 5～10h, it is thus achieved that described
Lithium manganese phosphate material, wherein said chosen atmosphere at least any one in air, nitrogen, argon hydrogen gaseous mixture atmosphere.
9. the lithium manganese phosphate material of a carbon cladding, it is characterised in that comprise: metal-doped the receiving of originally seeking peace described in claim 1
Rice porous chips lithium manganese phosphate material；And, it is coated with the carbon-coating of described nanoporous sheet lithium manganese phosphate material.
The lithium manganese phosphate material of carbon the most according to claim 9 cladding, it is characterised in that it comprises mass ratio is 0.5～10%:
The carbon of 1 and described lithium manganese phosphate material, and its tap density is 0.9～2g/cm3, 0.1C specific discharge capacity is at 140mAh g-1
Above.
The preparation method of the lithium manganese phosphate material that 11. carbon as according to any one of claim 9-10 are coated with, it is characterised in that including:
Take the metal doping nano porous chips lithium manganese phosphate material of originally seeking peace described in claim 1 to be dispersed in solvent with carbon source
And be sufficiently mixed, form the dispersion liquid of lithium manganese phosphate-carbon source, wherein carbon source and the quality of described nanoporous sheet lithium manganese phosphate material
Ratio is 5%～30%:1；Described carbon source at least selected from glucose, sucrose, fructose, soluble starch, Polyethylene Glycol, described molten
Agent includes water or ethanol；
By the dispersion liquid of described lithium manganese phosphate-carbon source at 100～120 DEG C, after 0.1～1h flash baking, at N2Or argon hydrogen gaseous mixture
Under atmosphere, 600～650 DEG C of heat treatments 3～5h, it is thus achieved that the lithium manganese phosphate sill of described carbon cladding.
12. 1 kinds of energy storage devices, it is characterised in that comprise the metal doping nano porous chips manganese phosphate of originally seeking peace described in claim 1
The lithium manganese phosphate material of the carbon cladding according to any one of lithium material or claim 9-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510125580.1A CN106159202A (en) | 2015-03-23 | 2015-03-23 | Originally seek peace metal doping nano porous chips lithium manganese phosphate material, its preparation method and application |
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| CN111564622A (en) * | 2020-07-14 | 2020-08-21 | 天能帅福得能源股份有限公司 | Lithium manganese iron phosphate cathode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007070A (en) * | 2008-04-14 | 2011-04-06 | 陶氏环球技术公司 | Lithium metal phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
| CN102142557A (en) * | 2010-01-29 | 2011-08-03 | 比亚迪股份有限公司 | Anode active material and preparation method thereof |
| KR20150015834A (en) * | 2013-08-01 | 2015-02-11 | 주식회사 엘지화학 | Anode active material comprising lithium manganese phosphate, preparation method thereof, and lithium secondary battery or hybrid capacitor comprising the same |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007070A (en) * | 2008-04-14 | 2011-04-06 | 陶氏环球技术公司 | Lithium metal phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
| CN102142557A (en) * | 2010-01-29 | 2011-08-03 | 比亚迪股份有限公司 | Anode active material and preparation method thereof |
| KR20150015834A (en) * | 2013-08-01 | 2015-02-11 | 주식회사 엘지화학 | Anode active material comprising lithium manganese phosphate, preparation method thereof, and lithium secondary battery or hybrid capacitor comprising the same |
Non-Patent Citations (1)
| Title |
|---|
| QINGBO XIA，等: ""High performance porous LiMnPO4 nanoflakes synthesis from a novel nanosheet precursor"", 《JOURNAL OF MATERIALS CHEMSISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111564622A (en) * | 2020-07-14 | 2020-08-21 | 天能帅福得能源股份有限公司 | Lithium manganese iron phosphate cathode material and preparation method thereof |
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