CN103311543A - Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof - Google Patents
Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof Download PDFInfo
- Publication number
- CN103311543A CN103311543A CN2013101759950A CN201310175995A CN103311543A CN 103311543 A CN103311543 A CN 103311543A CN 2013101759950 A CN2013101759950 A CN 2013101759950A CN 201310175995 A CN201310175995 A CN 201310175995A CN 103311543 A CN103311543 A CN 103311543A
- Authority
- CN
- China
- Prior art keywords
- anode material
- ion batteries
- ferric phosphate
- lithium ion
- gained
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
The invention discloses an anode material hydroxyl iron phosphate for lithium ion batteries and a preparation method thereof. The molecular formula of the anode material hydroxyl iron phosphate for lithium ion batteries is Fe1.5 (PO4) (OH); the anode material hydroxyl iron phosphate for the lithium ion batteries is prepared by using a hydrothermal synthesis method, i.e., the Fe1.5 (PO4) (OH) anode material with different morphologies and different electrochemical properties is obtained through adjusting different hydrothermal temperatures and pH values. Especially when the hydrothermal temperature is 150 DEG C and the pH is 2.5, the Fe1.5 (PO4) (OH) anode material is synthesized; when the charge and discharge rates are 0.1C and 0.3C, the first specific discharge capacities of the synthesized Fe1.5 (PO4) (OH) anode material are 176mAh/g and 154mAh/g, respectively; after 60 circulations, the specific discharge capacities are respectively kept at 165mAh/g and 150mAh/g. The preparation method has the characteristics of simple process, convenience in operation, applicability to large-scale production and the like.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries hydroxyl ferric phosphate and preparation method thereof.
Background technology
From Goodenough[1 in 1997] etc. reported LiFePO
4Reversible doff lithium characteristic since, the iron-based anode material for lithium-ion batteries is more extensive with its raw material sources, price is cheaper and non-environmental-pollution, the advantage such as environmental friendliness, Heat stability is good has received researcher's very big concern, is one of the most competitive person of Postive electrode material of li-ion accumulator of future generation.
In fact the iron-based anode material for lithium-ion batteries comprises two types, and a class is with LiFePO
4Be the positive electrode that contains lithium ion of main representative, another kind of then is the positive electrode that does not contain lithium ion.With FePO
4Be example, at LiFePO
4In the charging process, lithium ion and corresponding electronics are deviate from from material, thereby form new FePO in material
4Phase, and form boundary.In discharge process, lithium ion and corresponding electronics are embedded in the material, thereby at FePO
4The outside forms new LiFePO mutually
4Phase.Therefore, FePO
4Also can be used as anode material for lithium-ion batteries [2,3].
The hydroxyl ferric phosphate is a kind of mineral matter that extensively is present in occurring in nature, by a lot of mineralogist's broad research.The compound F 17-hydroxy-corticosterone e of Gheithi name tetragonal crystal system
2-y(PO4) (OH)
3y-2Be " lipscombite " [4].The people such as Whittinghan [5] have reported Fe
2-y y(PO4) (OH)
3y-2(H
2O)
3y-2Synthetic, the crystal structure of (represents the Fe room), chemical property and magnetic.
Hydroxyl ferric phosphate material has plurality of advantages as the positive electrode of lithium ion battery: (1) synthesis technique is simpler, owing to not having Fe (II) component in synthetic, does not need atmosphere protection, has saved corresponding equipment and cost and has dropped into; (2) hydroxyl ferric phosphate material synthesizes binary synthetic system, the control of more convenient synthesis condition and optimization; (3) because employing Fe (III) compound is raw material, make the synthesis material source wider.All these advantages can so that hydroxyl ferric phosphate material has more the advantage of low cost, large-scale production, be expected to become LiFePO
4The up-and-coming youngster of anode material for lithium-ion batteries.
But be Fe relevant for molecular formula not yet at present
1.5(PO
4) (OH) report of hydroxyl ferric phosphate material.
List of references
[1]、A.?Padhi,?K.?Nanjundaswamy,?J.B.?Goodenough,?Journal?of?the?Electrochemical?Society,?144?(1997)?1188-1194.
[2]、J.?Allen,?T.?Jow,?J.?Wolfenstine,?Journal?of?Solid?State?Electrochemistry,?12?(2008)?1031-1033.
[3]、P.?Reale,?B.?Scrosati,?C.?Delacourt,?C.?Wurm,?M.?Morcrette,?C.?Masquelier,?Chemistry?of?materials,?15?(2003)?5051-5058.
[4]、M.?Lindberg,?C.?Christ,?Acta?Crystallographica,?12?(1959)?695-697.
[5]、Y.?Song,?P.Y.?Zavalij,?N.A.?Chernova,?M.S.?Whittingham,?Chemistry?of?materials,?17?(2005)?1139-1147。
Summary of the invention
It is Fe that one of purpose of the present invention provides a kind of molecular formula
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.
It is Fe that two of the object of the invention provides above-mentioned a kind of molecular formula
1.5(PO
4) (OH) the preparation method of hydroxyl ferric phosphate lithium ion battery positive electrode.
Technical scheme of the present invention
A kind of anode material for lithium-ion batteries hydroxyl ferric phosphate adopts the hydrothermal synthesis method preparation, and its molecular formula is Fe
1.5(PO
4) (OH);
Described molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate is by FeO
6Octahedron respectively along [1 0 0] share with [0 1 0] crystal orientation coplanar and formation the stratiform chain and pass through FeO
4Tetrahedron respectively with adjacent two FeO
6Octahedron is shared a summit and two adjacent stratiform chains is coupled together a layer rhabdolith structure.
Above-mentioned a kind of anode material for lithium-ion batteries, namely molecular formula is Fe
1.5(PO
4) (OH) the synthetic method of hydroxyl ferric phosphate, specifically comprise the steps:
(1), at the Fe(NO of 0.02mol/L
3)
39H
2Add surfactant neopelex 0.0002mol/L in the O aqueous solution, then with the NH of 0.02mol/L
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, and electromagnetic agitation is even, with concentration be 15% ammoniacal liquor to be adjusted to pH be 1.5～4.5, then transfer in the hydrothermal reaction kettle, the control temperature is 150～200 ℃ and carries out hydro-thermal reaction 24h and get reactant liquor;
The Fe(NO of 0.02mol/L in the described mixed solution
3)
39H
2The NH of the O aqueous solution, 0.02mol/L
4H
2PO
4The amount of the aqueous solution and surfactant neopelex is pressed Fe
3+, PO
4 3-Calculate with the mol ratio of surfactant neopelex, i.e. Fe
3+: PO
4 3-: the surfactant neopelex is 1:1:0.01;
(2), with the reactant liquor of step (1) gained by centrifugation, the filter cake of gained adds absolute ethyl alcohol and cleans, the filter cake of final gained is heat-treated and obtained molecular formula is Fe
1.5(PO
4) (OH) anode material for lithium-ion batteries hydroxyl ferric phosphate;
Described heat treatment is about to filter cake and places quartz ampoule, in tube furnace successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min;
Described heat treatment process is carried out blasting under the environment of air.
Beneficial effect of the present invention
A kind of molecular formula proposed by the invention is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.Detect by experiment and find to have than iron-based anode material for lithium-ion batteries FePO
4Higher specific capacity and specific power, particularly hydrothermal temperature are 150 ℃, and the pH value is the Fe of 2.5 o'clock synthetic gained
1.5(PO
4) (OH) positive electrode be 0.1C at charge-discharge magnification, during 0.3C, its first discharge specific capacity is respectively 176mAh/g, 154mAh/g; Specific capacity remains on respectively 165mAh/g, 150mAh/g after 60 circulations.Therefore a kind of molecular formula of the present invention is Fe
1.5(PO
4) hydroxyl ferric phosphate lithium ion battery positive electrode (OH) can further improve the performance of lithium ion battery, so that lithium ion battery becomes possibility in the application of large-scale energy-storage battery.
Further, molecular formula of the present invention is Fe
1.5(PO
4) (OH) the preparation of hydroxyl ferric phosphate lithium ion battery positive electrode, owing to adopting hydrothermal synthesis method, therefore have preparation process simple, easy to operate, be suitable for the characteristics such as large-scale production.
Description of drawings
Fig. 1, embodiment 1,2,3 and 4 are the Fe that the pH value is 2.5, hydrothermal temperature is respectively 150 ℃, 170 ℃, 180 ℃ and 200 ℃ lower gained
1.5(PO
4) (OH) and the Fe of standard
1.5(PO
4) (OH) XRD collection of illustrative plates, wherein A is the Fe of standard
1.5(PO
4) (OH), B is the Fe of 150 ℃ of lower gained
1.5(PO
4) (OH), C is the Fe of 170 ℃ of lower gained
1.5(PO
4) (OH), D is the Fe of 180 ℃ of lower gained
1.5(PO
4) (OH), E is the Fe of 200 ℃ of lower gained
1.5(PO
4) (OH);
Fig. 2, embodiment 5,3,6,7 are that hydrothermal temperature is 180 ℃, and the pH value is respectively Fe synthetic under 1.5,2.5,3.5,4.5 the condition
1.5(PO
4) (OH) XRD collection of illustrative plates, wherein A is the Fe of standard
1.5(PO
4) (OH), B is that the pH value is the Fe of 1.5 times gained
1.5(PO
4) (OH), C is that the pH value is the Fe of 2.5 times gained
1.5(PO
4) (OH), D is that 1 pH value is the Fe of 3.5 times gained
1.5(PO
4) (OH), E is that the pH value is the Fe of 4.5 times gained
1.5(PO
4) (OH);
Fig. 3,200 ℃ of Fe that hydrothermal condition is synthetic
1.5(PO
4) (OH) XRD collection of illustrative plates, wherein A is the Fe of standard
1.5(PO
4) (OH), B is the Fe of 200 ℃ of lower gained
1.5(PO
4) (OH);
Fig. 4 A, Fe
1.5(PO
4) (OH) sample is along the crystal structure figure in [1 0 0] crystal orientation;
Fig. 4 B, Fe
1.5(PO
4) (OH) sample is along the crystal structure figure in [0 1 0] crystal orientation;
Fig. 5 A1 and Fig. 5 A2, embodiment 1 are that the pH value is 2.5, hydrothermal temperature is the Fe of 150 ℃ of lower gained
1.5(PO
4) (OH) SEM under different amplification figure;
Fig. 5 B1 and Fig. 5 B2, embodiment 2 are that the pH value is 2.5, hydrothermal temperature is the Fe of 170 ℃ of lower gained
1.5(PO
4) (OH) SEM under different amplification figure,
Fig. 5 C1, Fig. 5 C2 and Fig. 5 C3, embodiment 3 are that the pH value is 2.5, hydrothermal temperature is the Fe of 180 ℃ of lower gained
1.5(PO
4) (OH) SEM under different amplification figure,
Fig. 5 D1 and Fig. 5 D2, embodiment 4 are that the pH value is 2.5, hydrothermal temperature is the Fe of 200 ℃ of lower gained
1.5(PO
4) (OH) SEM under different amplification figure,
Fig. 6 A1 and Fig. 6 A2, embodiment 5 are that hydrothermal temperature is 180 ℃, and the pH value is synthetic Fe under 1.5 conditions
1.5(PO
4) (OH) the SEM collection of illustrative plates under different amplification;
Fig. 6 B1, Fig. 6 B2 and Fig. 6 B3, embodiment 3 are that hydrothermal temperature is 180 ℃, and the pH value is the Fe that synthesizes under 2.5 conditions under different amplification
1.5(PO
4) (OH) SEM collection of illustrative plates;
Fig. 6 C1, Fig. 6 C2 and Fig. 6 C3, embodiment 6 are that hydrothermal temperature is 180 ℃, and the pH value is the Fe that synthesizes under 3.5 conditions under different amplification
1.5(PO
4) (OH) SEM collection of illustrative plates;
Fig. 6 D1 and Fig. 6 D2, embodiment 7 are that hydrothermal temperature is 180 ℃, and the pH value is Fe synthetic under 4.5 the condition
1.5(PO
4) (OH) the SEM collection of illustrative plates under different amplification;
Fig. 7, embodiment 1,2,3 and 4 are the Fe that the pH value is 2.5, hydrothermal temperature is respectively 150 ℃, 170 ℃, 180 ℃ and 200 ℃ lower gained
1.5(PO
4) (OH) the first charge-discharge curve when 0.1C;
Fig. 8, embodiment 5,3,6,7 are that hydrothermal temperature is 180 ℃, and the pH value is respectively Fe synthetic under 1.5,2.5,3.5,4.5 the condition
1.5(PO
4) (OH) the first charge-discharge curve when 0.1C;
Fig. 9, embodiment 1,2,3 and 4 are the Fe that the pH value is 2.5, hydrothermal temperature is respectively 150 ℃, 170 ℃, 180 ℃ and 200 ℃ lower gained
1.5(PO
4) (OH) the cycle performance curve when 0.1C and 0.3C;
Figure 10, embodiment 5,3,6,7 are that hydrothermal temperature is 180 ℃, and the pH value is respectively Fe synthetic under 1.5,2.5,3.5,4.5 the condition
1.5(PO
4) (OH) the cycle performance curve when 0.1C and 0.3C.
Embodiment
Also by reference to the accompanying drawings the present invention is further set forth below by specific embodiment, but do not limit the present invention.
The preparation of positive electrode and the assembling of battery
The preparation of positive electrode
The present invention adopts the chemical property of CR2016 type button cell test material.
Calculate according to mass ratio, namely molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode: conductive agent is to use the planetary ball mill ball milling after the ratio of 75:17 is mixed, and adding an amount of alcohol is 500rad/min ball milling 2h at rotating speed, then puts into 120 ℃ of dry 12h of baking oven;
Wherein conductive agent is carbon black: graphite is pressed the mass ratio configuration of 6:4.
Accurately taking by weighing the good molecular formula of 0.0150g ball milling is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode and conductive agent composite material place agate mortar, drawing binding agent with microliter syringe is that ptfe emulsion adds wherein, and add and to be ground to after the absolute ethyl alcohol dilution driedly, making molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode and the full and uniform slurry that is mixed to get of binding agent;
Wherein, hydroxyl ferric phosphate and conductive agent composite material: ptfe emulsion adds for 92:8 in mass ratio, and the absolute ethyl alcohol addition is calculated in mass ratio, i.e. binding agent: absolute ethyl alcohol is the ratio of 1:100.
The slurry of gained after the above-mentioned grinding is applied on the stainless (steel) wire equably, and putting into behind 120 ℃ of dry 4h of baking oven at pressure is compacting under the 2Mpa, continues 3min, then puts into again dry 4h of 120 ℃ of baking ovens, namely obtains hydroxyl ferric phosphate positive pole sheet, prepares assembled battery.
The assembling of battery
Take lithium metal as negative pole, take the hydroxyl ferric phosphate positive pole sheet of above-mentioned gained as anodal, take porous polypropylene barrier film Celgard2400 as barrier film, electrolyte is: DMC:EMC:EC (1:1:1) is LiPF (W/W)
6Concentration 1.0M(Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City), the both positive and negative polarity battery case is that LIR2016 is assembled into button cell, and assembling process is at the glove box that is full of protective atmosphere (Ar gas) (the German M. Braun O of company
2＜0.1ppm, H
2O＜0.1ppm) finish in the glove box.
Put into after battery pack installs and finishes and carry out again electro-chemical test more than the static 3h of drier.
The physical characterization of material
Adopting Germany's (Bruker, D8 Advance) XRD powder diffractometer is Fe to the molecular formula of gained of the present invention
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode carries out material phase analysis, test condition: Cu
K ɑ=1.54056, voltage 40KV, electric current 200mA, 0.02 ° of step-length, 5 °/min of sweep speed, 10 °～90 ° of sweep limitss.
The molecular formula that adopts Japanese SU70 field emission scanning electron microscope FE-SEM to observe gained of the present invention is Fe
1.5(PO
4) (OH) pattern and the size of hydroxyl ferric phosphate lithium ion battery positive electrode.
The constant current charge-discharge test
The molecular formula of gained of the present invention is Fe
1.5(PO
4) (OH) the constant current charge-discharge performance test of hydroxyl ferric phosphate lithium ion battery positive electrode carries out in having programme controlled electro-chemical test equipment, that the present invention adopts is LAND battery test system CT2001A.
The charge-discharge test condition of battery is carried out under room temperature (25 ℃), and charge-discharge magnification is 0.1C and 0.3C, and the test voltage scope is 2.0～4.0V.
A kind of molecular formula is Fe
1.5(PO
4) (OH) the synthetic method of hydroxyl ferric phosphate lithium ion battery positive electrode, specifically comprise the steps:
(1), exists
50The Fe(NO of 0.02 mol/L of ml
3)
39H
2Add 0.348g surfactant neopelex in the O aqueous solution, then with the NH of the 0.02mol/L of 50ml
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, and electromagnetic agitation is even, with concentration be 15% ammoniacal liquor to be adjusted to pH be 2.5, then will transfer in the hydrothermal reaction kettle, the control temperature is 150 ℃ and carries out hydrothermal synthesis reaction 24h and get reactant liquor;
(2), with the reaction of step (1) gainedLiquid is transferred in the centrifuge tube,
The control rotating speed is5000
The centrifugal 10min of rpm,Then the upper strata stillness of night is outwelled, add absolute ethyl alcohol and clean, filter, repeat above-mentioned absolute ethyl alcohol cleaning, filter process 3 times, the filter cake of gained places quartz ampoule, under the condition of blowing air, in tube furnace successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min, under air conditions, heat-treat and can remove ammonium nitrate class impurity and the crystallization water, obtaining molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.
A kind of molecular formula is Fe
1.5(PO
4) (OH) the synthetic method of hydroxyl ferric phosphate lithium ion battery positive electrode, specifically comprise the steps:
(1), at the Fe(NO of the 0.02mol/L of 50ml
3)
39H
2Add 0.348g surfactant neopelex in the O aqueous solution, then with the NH of the 0.02mol/L of 50ml
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, and electromagnetic agitation is even, with concentration be 15% ammoniacal liquor to be adjusted to pH be 2.5, then transfer in the hydrothermal reaction kettle, the control temperature is 170 ℃ and carries out hydrothermal synthesis reaction 24h and get reactant liquor;
(2), the reactant liquor of step (1) gained is transferred in the centrifuge tube, the control rotating speed is the centrifugal 10min of 5000rpm, then the upper strata stillness of night is outwelled, adding absolute ethyl alcohol cleans, filters, repeat above-mentioned absolute ethyl alcohol cleaning, filter process 3 times, the filter cake of gained places quartz ampoule, under the condition of blowing air, in tube furnace successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min, under air conditions, heat-treat and can remove ammonium nitrate class impurity and the crystallization water, obtaining molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.
A kind of molecular formula is Fe
1.5(PO
4) (OH) the synthetic method of hydroxyl ferric phosphate lithium ion battery positive electrode, specifically comprise the steps:
(1), at the Fe(NO of the 0.02mol/L of 50ml
3)
39H
2Add 0.348g surfactant neopelex in the O aqueous solution, then with the NH of the 0.02mol/L of 50ml
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, and electromagnetic agitation is even, with concentration be 15% ammoniacal liquor to be adjusted to pH be 2.5, then transfer in the hydrothermal reaction kettle, the control temperature is 180 ℃ and carries out hydrothermal synthesis reaction 24h and get reactant liquor;
(2), the reactant liquor of step (1) gained is transferred in the centrifuge tube, the control rotating speed is the centrifugal 10min of 5000rpm, then the upper strata stillness of night is outwelled, adding absolute ethyl alcohol cleans, filters, repeat above-mentioned absolute ethyl alcohol cleaning, filter process 3 times, the filter cake of gained places quartz ampoule, under the condition of blowing air, in tube furnace successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min, under air conditions, heat-treat and can remove ammonium nitrate class impurity and the crystallization water, obtaining molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.
Embodiment 4
A kind of molecular formula is Fe
1.5(PO
4) (OH) the synthetic method of hydroxyl ferric phosphate lithium ion battery positive electrode, specifically comprise the steps:
(1), at the Fe(NO of the 0.02mol/L of 50ml
3)
39H
2Add 0.348g surfactant neopelex in the O aqueous solution, then with the NH of the 0.02mol/L of 50ml
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, and electromagnetic agitation is even, with concentration be 15% ammoniacal liquor to be adjusted to pH be 2.5, then transfer in the hydrothermal reaction kettle, the control temperature is 200 ℃ and carries out hydrothermal synthesis reaction 24h and get reactant liquor;
(2), the reactant liquor of step (1) gained is transferred in the centrifuge tube, the control rotating speed is the centrifugal 10min of 5000rpm, then the upper strata stillness of night is outwelled, adding absolute ethyl alcohol cleans, filters, repeat above-mentioned absolute ethyl alcohol cleaning, filter process 3 times, the filter cake of gained places quartz ampoule, under the condition of blowing air, in tube furnace successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min, under air conditions, heat-treat and can remove ammonium nitrate class impurity and the crystallization water, obtaining molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.
Embodiment 5
A kind of molecular formula is Fe
1.5(PO
4) (OH) the synthetic method of hydroxyl ferric phosphate lithium ion battery positive electrode, specifically comprise the steps:
(1), at the Fe(NO of the 0.02mol/L of 50ml
3)
39H
2Add 0.348g surfactant neopelex in the O aqueous solution, then with the NH of the 0.02mol/L of 50ml
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, and electromagnetic agitation is even, with concentration be 15% ammoniacal liquor to be adjusted to pH be 1.5, then with reactant transfer in hydrothermal reaction kettle, the control temperature is 180 ℃ and carries out hydrothermal synthesis reaction 24h and get reactant liquor;
(2), the reactant liquor of step (1) gained is transferred in the centrifuge tube, the control rotating speed is the centrifugal 10min of 5000rpm, then the upper strata stillness of night is outwelled, adding absolute ethyl alcohol cleans, filters, repeat above-mentioned absolute ethyl alcohol cleaning, filter process 3 times, the filter cake of gained places quartz ampoule, under the condition of blowing air, in tube furnace successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min, under air conditions, heat-treat and can remove ammonium nitrate class impurity and the crystallization water, obtaining molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.
A kind of molecular formula is Fe
1.5(PO
4) (OH) the synthetic method of hydroxyl ferric phosphate lithium ion battery positive electrode, specifically comprise the steps:
(1), at the Fe(NO of the 0.02mol/L of 50ml
3)
39H
2Add 0.348g surfactant neopelex in the O aqueous solution, then with the NH of the 0.02mol/L of 50ml
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, and electromagnetic agitation is even, with concentration be 15% ammoniacal liquor to be adjusted to pH be 3.5, then transfer in the hydrothermal reaction kettle, the control temperature is 180 ℃ and carries out hydrothermal synthesis reaction 24h and get reactant liquor;
(2), the reactant liquor of step (1) gained is transferred in the centrifuge tube, the control rotating speed is the centrifugal 10min of 5000rpm, then the upper strata stillness of night is outwelled, adding absolute ethyl alcohol cleans, filters, repeat above-mentioned absolute ethyl alcohol cleaning, filter process 3 times, the filter cake of gained places quartz ampoule, under the condition of blowing air, in tube furnace successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min, under air conditions, heat-treat and can remove ammonium nitrate class impurity and the crystallization water, obtaining molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.
A kind of molecular formula is Fe
1.5(PO
4) (OH) the synthetic method of hydroxyl ferric phosphate lithium ion battery positive electrode, specifically comprise the steps:
(1), at the Fe(NO of the 0.02mol/L of 50ml
3)
39H
2Add 0.348g surfactant neopelex in the O aqueous solution, then with the NH of the 0.02mol/L of 50ml
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, and electromagnetic agitation is even, with concentration be 15% ammoniacal liquor to be adjusted to pH be 4.5, then transfer in the hydrothermal reaction kettle, the control temperature is 180 ℃ and carries out hydrothermal synthesis reaction 24h and get reactant liquor;
(2), the reactant liquor of step (1) gained is transferred in the centrifuge tube, the control rotating speed is the centrifugal 10min of 5000rpm, then the upper strata stillness of night is outwelled, adding absolute ethyl alcohol cleans, filters, repeat above-mentioned absolute ethyl alcohol cleaning, filter process 3 times, the filter cake of gained places quartz ampoule, under the condition of blowing air, in tube furnace successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min, under air conditions, heat-treat and can remove ammonium nitrate class impurity and the crystallization water, obtaining molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode.
Fe to gained of the present invention
1.5
(PO
4
) (OH) XRD characterizes
Adopting Germany's (Bruker, D8 Advance) XRD powder diffractometer is Fe to the molecular formula of above-described embodiment 1～7 gained
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode carries out respectively material phase analysis, the test condition that analytic process adopts: Cu
K ɑ=1.54056, voltage 40KV, electric current 200mA, 0.02 ° of step-length, 5 °/min of sweep speed, 10 °～90 ° of sweep limitss.
Fig. 1 is respectively embodiment 1,2,3 and 4, the Fe that namely the pH value is 2.5, hydrothermal temperature is respectively 150 ℃, 170 ℃, 180 ℃ and 200 ℃ lower gained
1.5(PO
4) (OH) XRD collection of illustrative plates, Fig. 2 is respectively that embodiment 5,3,6,7 is that hydrothermal temperature is 180 ℃, the pH value is respectively synthetic Fe under 1.5,2.5,3.5,4.5 the condition
1.5(PO
4) (OH) XRD collection of illustrative plates.Contrast the JCPDS card as can be known, the Fe that synthesizes under each condition
1.5(PO
4) (OH) each main diffraction maximum and Fe
1.5(PO
4) (OH) standard diagram peak is corresponding, illustrates that it has higher purity and crystallinity, cell parameter is a=5.28, c=12.83.
As can be seen from Figure 1, the peak intensity of (1 0 3) crystal face raises along with the rising of hydrothermal temperature, illustrates that its crystallinity is also along with the temperature of hydro-thermal raises and raises.Yet, when beginning, the peak intensity of (4 0 0) crystal face raises along with the rising of hydrothermal temperature, and when hydrothermal temperature reached 200 ℃, its peak value reduced again.This may be that to begin along the growth of (4 0 0) crystal face be that rising along with hydrothermal temperature increases owing to crystal, and when temperature further raise, the growth of (4 0 0) crystal face was suppressed.
As can be seen from Figure 2, the peak intensity of (1 0 3) crystal face raises along with the rising of pH value, illustrates that its crystallinity also raises and raises along with the pH value.Yet, when beginning, the peak intensity of (4 0 0) crystal face raises along with the rising of pH value, and the pH value reaches at 4.5 o'clock, and its peak value reduces again.This may be that to begin along the growth of (4 0 0) crystal face be that rising along with pH value increases owing to crystal, and when the further increase of pH value, the growth of (4 0 0) crystal face is suppressed.
Fig. 3 is that embodiment 4 is Fe synthetic under 200 ℃ of conditions at hydrothermal temperature
1.5(PO
4) (OH) XRD collection of illustrative plates.As can be seen from Figure 3, its main component remains Fe
1.5(PO
4) (OH).Yet, showing on the XRD collection of illustrative plates, there is other dephasign in it.This is because hydrothermal temperature is too high, so that Fe
1.5(PO
4) (OH) transformation of crystal formation and structure occured.
Obtain Fe by materials studio5.0
1.5(PO
4) (OH) crystal structure figure such as Fig. 4 A of sample multi-angle, shown in Fig. 4 B.
Fig. 4 A, Fig. 4 B are respectively Fe
1.5(PO
4) (OH) along the crystal structure figure in [1 0 0] and [0 1 0] crystal orientation.The molecular formula that can find out gained of the present invention from Fig. 4 A, Fig. 4 B is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode is by FeO
6Octahedron respectively along [1 0 0] share with [0 1 0] crystal orientation coplanar and formation the stratiform chain and pass through FeO
4Tetrahedron respectively with adjacent two FeO
6Octahedron is shared a summit and two adjacent stratiform chains is coupled together a layer rhabdolith structure.
Fe to gained of the present invention
1.5
(PO
4
) (OH) SEM characterizes
Adopt Japanese SU70 field emission scanning electron microscope FE-SEM to observe embodiment 1～7 gained
Fe 1.5 (PO 4 ) (OH)The pattern of sample and size
Fig. 5 A1, Fig. 5 A2 are that embodiment 1 is that the pH value is 2.5, hydrothermal temperature is the Fe of 150 ℃ of lower gained
1.5(PO
4) (OH) SEM under different amplification figure, from Fig. 5 A1 as can be known, when hydrothermal temperature is 150 ℃, its granule-morphology is spherical, and particle size distribution is even, can find out from Fig. 5 A2, particle surface is relatively coarse, can find out by countless nano particle secondary agglomerations to form, regular shape, particle size be about 1 μ m.
Fig. 5 B1, Fig. 5 B2 are that embodiment 2 is that the pH value is 2.5, hydrothermal temperature is the Fe of 170 ℃ of lower gained
1.5(PO
4) (OH) SEM under different amplification figure, can find out from Fig. 5 B1, its pattern is a cube bulk, and its particle size distribution is even, can find out from Fig. 5 B2, and particle surface is smooth, and regular shape, particle size are about 4 μ m.
Fig. 5 C1, Fig. 5 C2, Fig. 5 C3 are that embodiment 3 is that the pH value is 2.5, hydrothermal temperature is the Fe of 180 ℃ of lower gained
1.5(PO
4) (OH) SEM under different amplification figure, can find out from Fig. 5 C1, its particle size distribution is even, can find out from Fig. 5 C2 and Fig. 5 C3, particle mainly contains two kinds of similar patterns, and a kind of is the dendritic structure that is formed by connecting by six arms with four ribs, the dendritic morphology that another kind is comprised of the arm that has four ribs more than six, the smooth densification of particle surface, regular shape, particle size are about 10 μ m.
Fig. 5 D1, Fig. 5 D2 are that embodiment 4 is that the pH value is 2.5, hydrothermal temperature is the Fe of 200 ℃ of lower gained
1.5(PO
4) (OH) SEM under different amplification figure, can find out that from Fig. 5 D1 its granule-morphology is that cross is forked, particle size distribution is even, can find out from Fig. 5 D2, it is to be about 5 μ m by 4, the spider that the arm of diameter 2 μ m forms, middle hollow, surface compact is smooth, and is irregular, and granular size is about 12 μ m.
Fig. 6 A1, Fig. 6 A2 are that embodiment 5 is that hydrothermal temperature is 180 ℃, and the pH value is Fe synthetic under 1.5 conditions
1.5(PO
4) (OH) the SEM collection of illustrative plates under different amplification, from Fig. 6 A1 as can be known, the pH value is 1.5 o'clock, its granule-morphology is spherical, and particle size distribution is even, can find out from Fig. 6 A2, particle surface is relatively coarse, it is to be formed by countless nano particle secondary agglomerations, and regular shape, particle size are about 4 μ m.
Fig. 6 B1, Fig. 6 B2, Fig. 6 B3 are that embodiment 3 is that hydrothermal temperature is 180 ℃, and the pH value is Fe synthetic under 2.5 conditions
1.5(PO
4) (OH) the SEM collection of illustrative plates under different amplification, can find out from Fig. 6 B1, its particle size distribution is even, can find out from Fig. 6 B2, particle mainly contains two kinds of similar patterns, and a kind of is the dendritic morphology that is formed by connecting by six arms with four ribs, the dendritic morphology that Fig. 6 B3 is comprised of the arm that has four ribs more than six, the smooth densification of particle surface, regular shape, particle size are about 10 μ m.
Fig. 6 C1, Fig. 6 C2, Fig. 6 C3 are that embodiment 6 is that hydrothermal temperature is 180 ℃, and the pH value is Fe synthetic under 3.5 conditions
1.5(PO
4) (OH) the SEM collection of illustrative plates under different amplification, from Fig. 6 C1 as can be known, its particle size distribution is even, can find out from Fig. 6 C2, and the quantity of its arm increases, and particle is larger, is about 15 μ m, can find out that from Fig. 6 C3 the surface is more fine and close.
Fig. 6 D1, Fig. 6 D2 are that embodiment 7 is that hydrothermal temperature is 180 ℃, and the pH value is Fe synthetic under 4.5 the condition
1.5(PO
4) (OH) the SEM collection of illustrative plates under different amplification, can draw from Fig. 6 D1, its granule-morphology is to be about 15 μ m by 4, the branch-and-leaf-shaped structure that diameter 4 μ m form with jagged arm, can find out from Fig. 6 D2, its surface compact, irregular, the side of its arm grows a large amount of branches, forms jagged arm, granular size is about 30 μ m, the relative pH of its branch-and-leaf-shaped arm quantity is minimizing in 2.5,3.5 o'clock, and this may be because pH continues to be elevated at 4.5 o'clock, suppressed crystal due to the growth of (4 0 0) crystal face, conclusion can be by Fig. 2 susceptible of proof.
Different pH values is to Fe in sum
1.5(PO
4) (OH) granule-morphology and the size of positive electrode have great impact.
Fig. 7 is that embodiment 1,2,3 and 4 is the Fe that the pH value is 2.5, hydrothermal temperature is respectively 150 ℃, 170 ℃, 180 ℃ and 200 ℃ lower gained
1.5(PO
4) (OH) the first charge-discharge curve chart when 0.1C.As can be seen from Figure 7, the Fe of embodiment 1,2,3 and 4 gained
1.5(PO
4) (OH) Fe
1.5(PO
4) (OH) positive electrode all have stably charge and discharge platform.Embodiment 1 is that hydrothermal temperature is 150 ℃, granule-morphology is spherical, particle size is that the positive electrode of 1 μ m has superior chemical property, its first discharge specific capacity reaches 176mAh/g, and under identical multiplying power, embodiment 2 is that hydrothermal temperature is 170 ℃ of (cube bulks, 4 μ m), embodiment 3 is that hydrothermal temperature is 180 ℃ of (dendroids, 10 μ m), embodiment 4 is that hydrothermal temperature is that the first discharge specific capacity of 200 ℃ (cross is forked, 12 μ m) is respectively 156mAh/g, 142mAh/g and 135mAh/g.In addition, specific discharge capacity is less in the time of 200 ℃, outside its reason particle-removing pattern and the size, also may be that its conclusion can be confirmed by Fig. 3 owing to there being other inactive dephasigns.
Fig. 8 is that embodiment 5,3,6,7 is that hydrothermal temperature is 180 ℃, and the pH value is respectively Fe synthetic under 1.5,2.5,3.5,4.5 the condition
1.5(PO
4) (OH) the first charge-discharge curve chart when 0.1C.As can be seen from Figure 8, embodiment 5 is that the pH value is 1.5 o'clock, and granule-morphology is spherical, particle size is that the positive electrode of 4 μ m has superior chemical property, and its first discharge specific capacity reaches 154mAh/g, and under identical multiplying power, embodiment 3 is that pH is the 2.5(dendroid, 10 μ m), embodiment 6 is the pH3.5(dendroid, 15 μ m), embodiment 7 is that the pH4.5(branch is lobate, 30 μ m) first discharge specific capacity is respectively 135mAh/g, 120mAh/g, 100mAh/g.
The result shows, embodiment 1 is that hydrothermal temperature is 150 ℃, and the pH value is respectively the spherical morphology of gained under 2.5 conditions and the molecular formula of small sized particles is Fe
1.5(PO
4) (OH) anode material for lithium-ion batteries has superior charge-discharge performance, this is because spheric granules and small sized particles material have larger specific area, for electrochemical reaction provides larger reaction interface.In addition, spheric granules and small size can shorten the diffusion path of lithium ion, have been conducive to improve the kinetics of diffusion performance of lithium ion in positive electrode.
Fe to gained of the present invention
1.5
(PO
4
) (OH) the cycle performance test of anode material for lithium-ion batteries
Adopt LAND battery test system CT2001A to embodiment 1～7 gained
Fe 1.5 (PO 4 ) (OH) anode material for lithium-ion batteries assembleBattery carries out charge-discharge test, and the charge-discharge test of battery carries out under room temperature (25 ℃), and charge-discharge magnification is 0.1C and 0.3C, and the test voltage scope is 2.0～4.0V, the results are shown in Figure 9, Figure 10.
Fig. 9 is that embodiment 1,2,3 and 4 is the Fe that the pH value is 2.5, hydrothermal temperature is respectively 150 ℃, 170 ℃, 180 ℃ and 200 ℃ lower gained
1.5(PO
4) (OH) the cycle performance curve chart when 0.1C and 0.3C, as can be seen from Figure 9, embodiment 1 is that the pH value is 2.5, synthetic Fe when hydrothermal temperature is 150 ℃
1.5(PO
4) (OH) sample is when discharge-rate is 0.1C, first discharge specific capacity is 176mAh/g, after 60 circulations, its specific discharge capacity still remains on 165mAh/g; When discharge-rate was 0.3C, first discharge specific capacity was 159mAh/g, still remained on 150mAh/g after 40 circulations.During other hydrothermal temperature, its cycle performance and high rate performance are also better.
Figure 10 is that embodiment 5,3,6,7 is that hydrothermal temperature is 180 ℃, and the pH value is respectively Fe synthetic under 1.5,2.5,3.5,4.5 the condition
1.5(PO
4) (OH) the cycle performance curve chart when 0.1C and 0.3C, as can be seen from Figure 10, embodiment 5 is that the pH value is 1.5 o'clock synthetic Fe
1.5(PO
4) (OH) sample is when discharge-rate is 0.1C, first discharge specific capacity is 154mAh/g, after 60 circulations, its specific discharge capacity still remains on 150mAh/g; When discharge-rate was 0.3C, first discharge specific capacity was 142mAh/g, still remained on 135mAh/g after 20 circulations.Under other pH condition, its cycle performance and high rate performance are also better.Show that thus molecular formula of the present invention is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode has good cycle performance and high rate performance.
In sum, the present invention is Fe by hydrothermal synthesis method acquisition molecular formula
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode, can obtain the anode material for lithium-ion batteries of various special appearances by regulating Hydrothermal Synthesis temperature and pH value.The Fe of spherical morphology and small sized particles particularly
1.5(PO
4) (OH) anode material for lithium-ion batteries have superior charge-discharge performance, this is because spheric granules and small-particulate materials have larger specific area, for electrochemical reaction provides larger reaction interface, in addition, spheric granules and small size can shorten the diffusion path of lithium ion, are conducive to improve the kinetics of diffusion performance of lithium ion in positive electrode.
Cycle performance test confirmation, molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode has good cycle performance and high rate performance.Therefore, molecular formula of the present invention is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate lithium ion battery positive electrode is a kind of Olivine-type Cathode Material in Li-ion Batteries with superior chemical property, has considerable application prospect.
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (4)
1. an anode material for lithium-ion batteries hydroxyl ferric phosphate is characterized in that described anode material for lithium-ion batteries is that molecular formula is Fe
1.5(PO
4) (OH) hydroxyl ferric phosphate, adopt the hydrothermal synthesis method preparation.
2. the synthetic method of a kind of anode material for lithium-ion batteries hydroxyl ferric phosphate as claimed in claim 1 is characterized in that specifically comprising the steps:
(1), at the Fe(NO of 0.02mol/L
3)
39H
2Add the surfactant neopelex in the O aqueous solution, then with the NH of 0.02mol/L
4H
2PO
4The aqueous solution is poured into and is wherein obtained mixed solution, stir, with concentration be 15% ammoniacal liquor to be adjusted to pH be 1.5～4.5, then be transferred in the hydrothermal reaction kettle, the control temperature is 150～200 ℃ and carries out hydrothermal synthesis reaction 24h and obtain reactant liquor;
The Fe(NO of 0.02mol/L in the described mixed solution
3)
39H
2The NH of the O aqueous solution, 0.02mol/L
4H
2PO
4The amount of the aqueous solution and surfactant neopelex is pressed Fe
3+, PO
4 3-Calculate with the mol ratio of surfactant neopelex, i.e. Fe
3+: PO
4 3-: the surfactant neopelex is 1:1:0.01;
(2), with the reactant liquor of step (1) gained by centrifugation and add absolute ethyl alcohol and clean, the filter cake of gained is heat-treated under the condition that air exists the most at last, obtains anode material for lithium-ion batteries hydroxyl ferric phosphate.
3. the synthetic method of a kind of anode material for lithium-ion batteries hydroxyl ferric phosphate as claimed in claim 2 is characterized in that the Hydrothermal Synthesis temperature described in the step (1) is 150 ℃, and the pH value is 2.5.
4. the synthetic method of a kind of anode material for lithium-ion batteries hydroxyl ferric phosphate as claimed in claim 3, it is characterized in that the heat treatment described in the step (2), be about to filter cake and place quartz ampoule, in tube furnace, under the condition that air exists successively with 120 ℃ of sintering 1h, 160 ℃ of sintering 1h, 400 ℃ of sintering 3h, and each temperature-rise period control programming rate is 3 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101759950A CN103311543A (en) | 2012-12-10 | 2013-05-14 | Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210524637.1 | 2012-12-10 | ||
| CN201210524637 | 2012-12-10 | ||
| CN2013101759950A CN103311543A (en) | 2012-12-10 | 2013-05-14 | Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103311543A true CN103311543A (en) | 2013-09-18 |
Family
ID=49136521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101759950A Pending CN103311543A (en) | 2012-12-10 | 2013-05-14 | Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103311543A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105024073A (en) * | 2015-08-10 | 2015-11-04 | 河南理工大学 | Cathode material Fe<2.95>(PO4)2(OH)2 of lithium ion battery and preparation method thereof |
| CN105236375A (en) * | 2015-09-17 | 2016-01-13 | 上海第二工业大学 | Method for preparing hydrated hydroxyl ferric phosphates by utilizing waste phosphatization slag for extraction |
| CN105406035A (en) * | 2015-10-30 | 2016-03-16 | 上海应用技术学院 | Preparation method for regular octahedron-shaped iron phosphate/graphene oxide precursor |
| CN105417517A (en) * | 2015-11-03 | 2016-03-23 | 山东精工电子科技有限公司 | Tremelliform ferric phosphate and preparation method therefor |
| CN105470504A (en) * | 2014-09-29 | 2016-04-06 | 住友大阪水泥股份有限公司 | Cathode material, method for producing cathode materials, cathode, and lithium ion battery |
| CN106340645A (en) * | 2016-09-08 | 2017-01-18 | 西北工业大学 | Preparation method of hydroxyl iron phosphate-based battery material with novel morphology |
| CN106517130A (en) * | 2016-12-27 | 2017-03-22 | 合肥学院 | Method for preparing iron hydroxyphosphate micro-nano powder material from phosphorus-rich biomass |
| CN106848280A (en) * | 2017-01-17 | 2017-06-13 | 陕西科技大学 | A kind of preparation method of the hollow octahedra anode material for lithium-ion batteries of graphene-supported di iron |
| CN109494367A (en) * | 2018-11-28 | 2019-03-19 | 河南科技学院 | Di iron lithium/grapheme composite positive electrode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102403501A (en) * | 2011-11-24 | 2012-04-04 | 上海电力学院 | Method for preparation of cathode material spherical FePO4 of lithium-ion battery |
-
2013
- 2013-05-14 CN CN2013101759950A patent/CN103311543A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102403501A (en) * | 2011-11-24 | 2012-04-04 | 上海电力学院 | Method for preparation of cathode material spherical FePO4 of lithium-ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 王忠丽: "铁基磷酸盐正极材料的研究", 《中国博士学位论文全文数据库工程科技II辑》, no. 8, 15 August 2009 (2009-08-15), pages 042 - 35 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470504A (en) * | 2014-09-29 | 2016-04-06 | 住友大阪水泥股份有限公司 | Cathode material, method for producing cathode materials, cathode, and lithium ion battery |
| CN105024073B (en) * | 2015-08-10 | 2017-08-25 | 河南理工大学 | Anode material for lithium-ion batteries di iron and preparation method thereof |
| CN105024073A (en) * | 2015-08-10 | 2015-11-04 | 河南理工大学 | Cathode material Fe<2.95>(PO4)2(OH)2 of lithium ion battery and preparation method thereof |
| CN105236375A (en) * | 2015-09-17 | 2016-01-13 | 上海第二工业大学 | Method for preparing hydrated hydroxyl ferric phosphates by utilizing waste phosphatization slag for extraction |
| CN105406035A (en) * | 2015-10-30 | 2016-03-16 | 上海应用技术学院 | Preparation method for regular octahedron-shaped iron phosphate/graphene oxide precursor |
| CN105406035B (en) * | 2015-10-30 | 2018-03-13 | 上海应用技术学院 | A kind of preparation method of regular octahedron type ferric phosphate/graphene oxide presoma |
| CN105417517B (en) * | 2015-11-03 | 2018-01-02 | 山东精工电子科技有限公司 | A kind of tremelliform ferric phosphate and preparation method thereof |
| CN105417517A (en) * | 2015-11-03 | 2016-03-23 | 山东精工电子科技有限公司 | Tremelliform ferric phosphate and preparation method therefor |
| CN106340645A (en) * | 2016-09-08 | 2017-01-18 | 西北工业大学 | Preparation method of hydroxyl iron phosphate-based battery material with novel morphology |
| CN106517130A (en) * | 2016-12-27 | 2017-03-22 | 合肥学院 | Method for preparing iron hydroxyphosphate micro-nano powder material from phosphorus-rich biomass |
| CN106848280A (en) * | 2017-01-17 | 2017-06-13 | 陕西科技大学 | A kind of preparation method of the hollow octahedra anode material for lithium-ion batteries of graphene-supported di iron |
| CN106848280B (en) * | 2017-01-17 | 2019-05-21 | 陕西科技大学 | A kind of preparation method of the hollow octahedra anode material for lithium-ion batteries of graphene-supported di iron |
| CN109494367A (en) * | 2018-11-28 | 2019-03-19 | 河南科技学院 | Di iron lithium/grapheme composite positive electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103311543A (en) | Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof | |
| US8133616B2 (en) | Lithium manganese phosphate positive material for lithium secondary battery | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN101630739B (en) | Preparation method of modified doping lithium ferric phosphate | |
| CN103956485B (en) | Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof | |
| Zhao et al. | Solution combustion synthesis of high-rate performance carbon-coated lithium iron phosphate from inexpensive iron (III) raw material | |
| CN101114709A (en) | Lithium ion battery composite anode material LiFePO4-Li3V2(PO4)3/C and method for making same | |
| CN101820062B (en) | Multi-solvent preparation method of lithium iron phosphate | |
| CN113526483B (en) | Ferro-phosphorus sodalite type cathode material and preparation method and application thereof | |
| CN101013751A (en) | Ball-shaped lithium-ion battery anode material doped with rare earth and method for making same | |
| CN102447096B (en) | Lithium ferrovanadium phosphate solid solution for positive material of lithium ion battery and preparation and application thereof | |
| CN102569792A (en) | Preparation method for one-step synthesis of high-rate-performance carbon-coated lithium iron phosphate cathode material by in-situ hydrothermal carbonization | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| CN103208626A (en) | Method for preparing lithium iron phosphate/carbon composite material by using aniline | |
| CN104638261A (en) | High rate LiFePO4/C positive electrode material and preparation method thereof | |
| CN102464309A (en) | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide | |
| CN104009234B (en) | The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium | |
| CN103413918B (en) | A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium | |
| CN102208624A (en) | Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method | |
| CN111490240A (en) | Aqueous lithium ion battery and application thereof | |
| CN102097615A (en) | Method for preparing LiFePO4/C composite anode material of lithium ion battery | |
| CN102299318B (en) | Preparation method of positive electrode material LiFePO4 for lithium ion battery | |
| CN102447099B (en) | New method for preparing lithium ferrous phosphate double-salt anode material by using iron chippings, phosphoric acid and lithium hydroxide | |
| CN103066286A (en) | Vanadium-antimony co-doped lithium iron phosphate used as lithium ion positive pole material and preparation method thereof | |
| CN103326021B (en) | The preparation method of lithium iron phosphate cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130918 |