CN101841039A - Cathode material ferric phosphate doped with metallic ions for lithium ion battery and preparation method thereof - Google Patents
Cathode material ferric phosphate doped with metallic ions for lithium ion battery and preparation method thereof Download PDFInfo
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- CN101841039A CN101841039A CN201010165276A CN201010165276A CN101841039A CN 101841039 A CN101841039 A CN 101841039A CN 201010165276 A CN201010165276 A CN 201010165276A CN 201010165276 A CN201010165276 A CN 201010165276A CN 101841039 A CN101841039 A CN 101841039A
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Abstract
The invention discloses a cathode material ferric phosphate doped with metallic ions for a lithium ion battery and a preparation method thereof. The ferric phosphate doped with the metallic ions consists of a Fe source, a P source and the doped metallic ions, wherein a mol ratio of the Fe source to the doped metallic ions to the P source is 0.92-0.99: 0.01-0.08: 1. A wet synthesis method or a solid-phase synthesis method is adopted to prepare the cathode material ferric phosphate doped with the metallic ions for the lithium ion battery by doping the metallic ions. The doping of the ions is proved to play a positive role in the electrochemical properties of the ferric phosphate material in a way that the capacity of the ferric phosphate material doped with the metallic ions is improved by 10 to 50 percent than that of the ferric phosphate material not doped with the metallic ions. Through the doping of the ions, the electronic conductivity of the material is improved; and simultaneously, due to differences in radiuses of the coped ions, crystal structures of the ferric phosphate are changed, which is favorable for the migration and diffusion of lithium ions.
Description
Technical field
The present invention relates to the material of chemical power source, more particularly relate to ferric phosphate of anode material for lithium-ion batteries-doped metal ion and preparation method thereof.
Background technology
The energy is that the mankind depend on for existence and the important substance basis of social development, is the important foundation stone of national economy, national security and realization sustainable development.At present, the novel high-energy chemical power source of green non-pollution has become competitively hot of research and development of countries in the world.Theory and practice proves that lithium ion battery has the incomparable advantage of other secondary cells, and the superiority of lithium ion battery can reduce basically: operating voltage height (be Ni-MH battery 3 times); Specific energy big (can reach 180Wh/kg, be 3 times of Ni-H cell); Volume is little; Light weight; Have extended cycle life; Self-discharge rate is low; Memory-less effect; Pollution-free etc.Under the more and more severeer situation of global energy and environmental problem, lithium ion battery is high-power to using, the application apparatus of macro-energy provides new selection.The notion of the intelligent grid of U.S.'s proposition especially in recent years quickens to have advanced the development of new forms of energy, the development of intelligent grid can insert in the electrical network all kinds of energy-storage units better, and the interaction of realization energy, new vitality has been injected in this development for the Another application focus-electric automobile of present chemical power source.Employed chemical power source not only can be used for the energy of automobile in the electric automobile, can also be the energy-storage units in the electrical network, plays the effect of peak load shifting and regulated power quality.LiFePO4 is that the lithium ion battery of positive pole is wide owing to its raw material sources, environmental friendliness, and advantages such as stable performance have become the good lithium ion battery in each field.But still there are many deficiencies in lithium iron phosphate positive material, is mainly reflected in the product batches instability; and owing to contain ferrous iron in the LiFePO4; making all must have inert atmosphere protection in the whole synthesis technique, has increased production cost, has restricted this Development of Materials.From existing research, ferric phosphate also has higher electro-chemical activity as the positive electrode of lithium ion battery, and under the low range discharging condition, specific capacity can reach 130mAh/g.
FePO
4Material has plurality of advantages as the positive electrode of lithium ion battery: (i) synthesis technique is simpler, owing to do not have Fe (II) component in synthetic, does not need atmosphere protection, has saved corresponding apparatus and input; (ii) FePO
4Material synthesize the binary synthetic system, be convenient to control and optimize synthesis condition; (iii), make the synthesis material source wider because employing Fe (III) compound is a raw material.All these advantages can make FePO
4Material has more the advantage of low cost, large-scale production, if be the positive electrode of lithium ion battery with the ferric phosphate directly, then is expected to become the up-and-coming youngster of iron-based anode material for lithium-ion batteries.Yet in the research of lithium ion battery positive pole material phosphoric acid iron, find that ferric phosphate is relatively poor aspect electron conduction and ionic conductivity, seriously restricted the application of this material.
Summary of the invention
One of purpose of the present invention proposes a kind of ferric phosphate of anode material for lithium-ion batteries-doped metal ion in order to address the above problem.
Two of purpose of the present invention provides the preparation method of ferric phosphate of above-mentioned a kind of anode material for lithium-ion batteries-doped metal ion.
The modification technology of lithium ion anode material ferric phosphate.By ferric phosphate is carried out the ion doping modification, improve ferric phosphate in the method as the conductivity in the battery material.And then the application of promotion ferric phosphate in lithium ion battery.
Technical scheme of the present invention
By doped metal ion, can improve the structure and the semiconducting behavior of ferric phosphate, improve the electron conduction and the ionic conducting property of this material, make it in battery charging and discharging, have higher discharge-rate and discharge capacity.On doping method, make dopant ion to be blended in the precursor uniformly by solid phase synthesis or liquid phase are synthetic, and enter in the ferric phosphate character by sintering.
A kind of ferric phosphate of anode material for lithium-ion batteries-doped metal ion, the mol ratio of Fe wherein: doped metal ion: P are 0.92～0.99: 0.01～0.08: 1, and wherein doped metal ion is Al
3+, Cr
3+, Cu
2+Or Ce
3+
The co-precipitation preparation method of the ferric phosphate of above-mentioned a kind of anode material for lithium-ion batteries-doped metal ion comprises being prepared as follows step:
(1), the mixing of raw material
Phosphorus source, source of iron and doped metal ion are joined dissolving mixing in the container that fills pure water, form phosphorus source, source of iron and doped metal ion raw mix;
Described phosphorus source is the phosphate or the phosphoric acid of solubility; Wherein the phosphate of solubility is (NH
4)
2HPO
4Or NH
4H
2PO
4
Wherein source of iron is carbonate, acetate, nitrate, the oxide of iron or the hydroxide of iron of iron;
Wherein doped metal ion is Al
3+, Cr
3+, Cu
2+Or Ce
3+Soluble-salt or hydroxide or oxide; Al
3+, Cr
3+, Cu
2+Or Ce
3+Soluble-salt be Al
3+, Cr
3+, Cu
2+Or Ce
3+Nitrate or acetate;
(2), the preparation of the precursor of the ferric phosphate of doped metal ion
Is under 20～100 ℃ with the raw mix of phosphorus, iron and the doped metal ion of step (1) gained in temperature, gets the precursor of the ferric phosphate of doped metal ion by co-precipitation or sol-gel process;
(3), the preparation of the ferric phosphate of doped metal ion
Ferric phosphate precursor to the doped metal ion of step (2) gained washs, filters, then it is heat-treated, promptly control temperature at 300～600 ℃, in air 5 hours, sieve after crushed again, promptly form the ferric phosphate of the positive electrode-doped metal ion of lithium ion battery of the present invention.
The solid phase synthesis preparation method thereof of the ferric phosphate of above-mentioned a kind of anode material for lithium-ion batteries-doped metal ion comprises being prepared as follows step:
(1), the ball milling of raw material mixes
Phosphorus source, source of iron and doped metal ion are carried out ball milling mix, form phosphorus source, source of iron and doped metal ion raw mix;
Described phosphorus source is ammonium phosphate or diammonium hydrogen phosphate or phosphoric acid;
Wherein source of iron is di-iron trioxide, ferric carbonate or ferric acetate;
Wherein doped metal ion is Al
3+, Cr
3+, Cu
2+Or Ce
3+Salt or hydroxide or oxide; Al
3+, Cr
3+, Cu
2+Or Ce
3+Salt be Al
3+, Cr
3+, Cu
2+Or Ce
3+Carbonate, nitrate or acetate;
(2), the preparation of the ferric phosphate of doped metal ion
To heat-treat by the mixed compound of ball milling in the step (1), promptly control temperature at 300～600 ℃, sintering is 5 hours in air, sieves after crushed again, promptly forms the ferric phosphate of the positive electrode-doped metal ion of lithium ion battery of the present invention.
Beneficial effect of the present invention
The ferric phosphate of a kind of anode material for lithium-ion batteries-doped metal ion of the present invention, because doped metal ion, the ferric phosphate of the anode material for lithium-ion batteries-doped metal ion of gained is compared its capacity with the ferric phosphate material of doped metal ion not and has been improved 10%～50%, and the doping that ion is described has been played positive effect to the chemical property of ferric phosphate material.The doping of ion does not change the structure (as Fig. 9) of material, but the doping of ion has improved the electron conduction of material, as shown in figure 10, helps the migration and the diffusion of lithium ion.
Description of drawings
Fig. 1, unadulterated FePO
4Charging and discharging curve
Fig. 2, doped with Al
3+The charging and discharging curve of FePO4 positive electrode
Fig. 3, doping Cr
3+The FePO of ion
4The charging and discharging curve of material
Fig. 4, doped with Cu
2+The FePO of ion
4The charging and discharging curve of material
Fig. 5, doped Ce
3+The FePO of ion
4The charging and discharging curve of material
The doping Cr of Fig. 6, different sintering temperatures
3+The FePO of ion
4The charging and discharging curve of material
The doping Cr of Fig. 7, different sintering temperatures
3+The FePO of ion
4The XRD figure of material
Fig. 8,, different concentration of Ce
3+The FePO of ions dosage
4The charging and discharging curve of material
The XRD spectrum of the ferric phosphate material of Fig. 9, different dopant ions
The electrochemical impedance spectroscopy of the ferric phosphate electrode of Figure 10, different dopant ions
Embodiment
Below by embodiment the present invention is further set forth, but do not limit the present invention.
The FePO that mixes
4Electrode and battery preparation method, step is as follows:
(1), the preparation of ferric phosphate electrode: the employing doped iron phosphate is a positive electrode, also need add electronic conductive material (as graphite, carbon black, acetylene black, metal dust or other conducting polymer composites etc.) and binding agent (as Kynoar, polytetrafluoroethylene, cellulose, water-soluble rubber etc.) in the preparation of positive plate.Ratio between each component is counted according to quality: ferric phosphate: electronic conductive material: binding agent=70～80: 10～20: 5～10; Negative pole adopts metal lithium sheet.
(2), battery assembling: electrolyte adopts the rare ester of ethylene: the Methylethyl carbonic ester: diethyl carbonate=1: 1: 1 (wt%) is a solvent, with the hexafluoro phosphorus lithium (LiPF of 1mol/L
6) be electrolyte solution.
With the ferric phosphate pole piece is positive pole, and the lithium sheet is a negative pole, is assembled into battery.
The characterization parameter condition determination of battery behavior
With the electrochemical impedance of electrochemical impedance spectroscopy mensuration button cell, the conductivity of comparative material.Analyze the structure of various materials with x-ray diffractometer.
The charge-discharge test condition of battery
High charge is pressed and is 4V, and minimum discharge voltage is 2.5V.The charge-discharge test of battery at room temperature (about 25 ℃) is finished, and charge-discharge magnification is 0.1C.
Example 1
Pure FePO
4Preparation, adopt coprecipitation
Fe: 1: 1 proportioning of P mol ratio takes by weighing Fe (NO
3)
39H
2O, NH
4H
2PO
4, after the water-soluble mixing of above-mentioned each material, mechanical agitation, regulating pH is 2.5, is heated to 90 ℃, reacts after 10 hours, ageing is filtered, washing, the dry precursor that obtains.Under 380 ℃, sintering is 10 hours in air with precursor, then by sieving after the ball mill grinding, promptly gets the ferric phosphate material of a kind of anode material for lithium-ion batteries-metal ion that undopes.With this material is positive pole, is negative pole with the lithium sheet, is assembled into battery, carries out charge-discharge test.Fig. 1 is the FePO of doped metal ion not
4The battery charging and discharging curve.
Example 2
With Al
3+Ion doping adopts solid phase synthesis
With Fe: Al: 0.96: 0.04: 1 proportioning of P mol ratio takes by weighing Fe
2(CO
3)
3, Al (NO
3)
39H
2O and (NH
4)
2HPO
4, after above-mentioned each material mixed, be that medium carries out ball milling with ethanol, the time is 12 hours, then with mixture under 380 ℃, sintering is 10 hours in air, then, by ball mill grinding, promptly gets a kind of anode material for lithium-ion batteries-doped with Al
3+The ferric phosphate synthetic material of ion.
With this synthetic material is positive pole, is negative pole with the lithium sheet, is assembled into battery, carries out electro-chemical test and charge-discharge test.Fig. 2 is battery charging and discharging curve, as can be seen from Figure 2 Al
3+Behind the ion doping, with respect to the unadulterated ferric phosphate material of Fig. 1, the capacity of ferric phosphate material is increased to 93mAh/g by original 73mAh/g.Al is described
3+After the doping of ion, in the ferric phosphate charge and discharge process, the Fe ion constantly changes with charging and discharge in charge and discharge process, and Al
3+Ionic valence condition does not change, and can change Fe in the ferric phosphate charge and discharge process (II) PO like this
4/ Fe (III) PO
4The charge structure at interface helps improving the electrical conductance of material.Compare its capacity by the ferric phosphate material after mixing with unadulterated ferric phosphate material and improved 27%, illustrate that aluminum ions doping played positive effect to the chemical property of ferric phosphate material.
Example 3
With Cr
3+Ion doping adopts collosol and gel synthetic
With Fe: Cr: 0.96: 0.04: 1 proportioning of P mol ratio takes by weighing ferric acetate, Cr (NO
3)
39H
2O and NH
4H
2PO
4, after the water-soluble mixing of above-mentioned each material, and adding citric acid, after the mechanical agitation, regulating pH is 2.5, is heated to 80 ℃, the evaporation back forms gel, the dry precursor that obtains.Under 550 ℃, sintering is 10 hours in air with precursor, then by sieving after the ball mill grinding, promptly gets a kind of anode material for lithium-ion batteries-doping Cr
3+The ferric phosphate synthetic material of ion.With this synthetic material is positive pole, is negative pole with the lithium sheet, is assembled into battery, carries out electro-chemical test and charge-discharge test.
Fig. 3 is battery charging and discharging curve, as can be seen from Figure 3 Cr
3+Behind the ion doping, with respect to the unadulterated ferric phosphate material of Fig. 1, the capacity of ferric phosphate material is increased to 110mAh/g by original 73mAh/g.Cr is described
3+After the doping of ion, improved the charge/discharge capacity of ferric phosphate greatly.In the ferric phosphate charge and discharge process, the Fe ion constantly changes Cr with charging and discharge in charge and discharge process
3+Ionic valence condition also can change, but changing pairing current potential difference can change Fe in the ferric phosphate charge and discharge process (II) PO like this
4/ Fe (III) PO
4The charge structure at interface helps improving the electrical conductance of material.Simultaneously, because Cr
3+/ Cr
2+The ionic radius of ion is also respectively greater than Fe
3+/ Fe
2+Ion can further improve the lattice structure of ferric phosphate like this, widened the passage of lithium ion embedding-move out.The conductivity that more helps material.Compare its capacity by the ferric phosphate material after mixing with unadulterated ferric phosphate material and improved 50%, Cr is described
3+The doping of ion has been played positive effect to the chemical property of ferric phosphate material.
Example 4
Control different sintering temperatures, promptly be respectively under 380 ℃, the 460 ℃ conditions, other conditions are with embodiment 3, the doping Cr that makes respectively
3+The ferric phosphate synthetic material of ion.
Respectively with the doping Cr of above-mentioned gained
3+Ferric phosphate synthetic material and embodiment 3 sintering temperatures be the doping Cr of 550 ℃ of following gained
3+The ferric phosphate synthetic material of ion is anodal, is negative pole with the lithium sheet, is assembled into battery, carries out electro-chemical test and charge-discharge test.The charging and discharging curve of gained and XRD figure are seen Fig. 6, Fig. 7 respectively.As can be seen, different heat treatment temperatures has certain influence to the capacity of material from Fig. 6 and Fig. 7, and too high heat treatment temperature can make the ferric phosphate grain growth, even vitrifying, makes activity reduce greatly; Too low temperature is unfavorable for that then dopant ion enters in the ferric phosphate lattice, and its modified effect can be relatively poor.
Example 5
With Cu
2+Ion doping adopts coprecipitation synthetic
With Fe: Cu: 0.96: 0.04: 1 proportioning of P mol ratio is measured Fe
2(CO
3)
3, Cu (NO
3)
2And H
3PO
4, after the water-soluble mixing of above-mentioned each material, mechanical agitation, regulating pH is 2.5, is heated to 90 ℃, reacts after 10 hours, ageing is filtered, washing, the dry precursor that obtains.Under 380 ℃, sintering is 10 hours in air with precursor, then by sieving after the ball mill grinding, promptly gets a kind of anode material for lithium-ion batteries-doped with Cu
2+The ferric phosphate synthetic material of ion.With this synthetic material is positive pole, is negative pole with the lithium sheet, is assembled into battery, carries out electro-chemical test and charge-discharge test.Fig. 4 is battery charging and discharging curve, as can be seen from Figure 4 Cu
2+Behind the ion doping, with respect to the unadulterated ferric phosphate material of Fig. 1, the capacity of ferric phosphate material is increased to 83mAh/g by original 73mAh/g.Cu is described
2+After the doping of ion, improved the charge/discharge capacity of ferric phosphate, in the ferric phosphate charge and discharge process, the Fe ion constantly changes with charging and discharge in charge and discharge process, and Cu
2+Ionic valence condition does not change, and can change Fe in the ferric phosphate charge and discharge process (II) PO like this
4/ Fe (III) PO
4The charge structure at interface helps improving the electrical conductance of material.Simultaneously, because Cu
2+The ionic radius of ion is also respectively greater than Fe
2+/ Fe
3+Ion can further improve the lattice structure of ferric phosphate like this, widened the passage of lithium ion embedding-move out.The conductivity that more helps material.Compare its capacity by the ferric phosphate material after mixing with unadulterated ferric phosphate material and improved 14%, the doping that ion is described has been played positive effect to the chemical property of ferric phosphate material.
Example 6
With Ge
3+Ion doping adopts co-precipitation synthetic
With Fe: Ce
3+: 0.96: 0.04: 1 proportioning of P mol ratio takes by weighing Fe (NO
3)
39H
2O, Ce (NO
3)
3And NH
4H
2PO
4, after the water-soluble mixing of above-mentioned each material, mechanical agitation, regulating pH is 2.5, is heated to 90 ℃, reacts after 10 hours, ageing is filtered, washing, the dry precursor that obtains.Under 380 ℃, sintering is 10 hours in air with precursor, then by sieving after the ball mill grinding, promptly gets a kind of anode material for lithium-ion batteries-doped Ce
3+The ferric phosphate synthetic material of ion.With this synthetic material is positive pole, is negative pole with the lithium sheet, is assembled into battery, carries out electro-chemical test and charge-discharge test.Fig. 5 is battery charging and discharging curve, as can be seen from Figure 5 Ce
3+Behind the ion doping, with respect to the unadulterated ferric phosphate material of Fig. 1, the capacity of ferric phosphate material is increased to 108mAh/g by original 73mAh/g.Ce is described
3+After the doping of ion, improved the charge/discharge capacity of ferric phosphate greatly.In the ferric phosphate charge and discharge process, the Fe ion constantly changes Ce with charging and discharge in charge and discharge process
3+Ionic valence condition also can change, but changes pairing current potential difference, can change Fe in the ferric phosphate charge and discharge process (II) PO like this
4/ Fe (III) PO
4The charge structure at interface helps improving the electrical conductance of material.Simultaneously, because Ce
3+/ Ce
4+The ionic radius of ion is also respectively greater than Fe
3+/ Fe
2+Ion can further improve the lattice structure of ferric phosphate like this, widened the passage of lithium ion embedding-move out.The conductivity that more helps material.Compare its capacity by the ferric phosphate material after mixing with unadulterated ferric phosphate material and improved 50%, the doping that ion is described has been played positive effect to the chemical property of ferric phosphate material.
Example 7
Control Fe: Ce
3+: the P mol ratio was respectively 0.98: 0.02: 1; 0.94: under 0.06: 1 and 0.92: 0.08: 1 condition, other conditions make a kind of anode material for lithium-ion batteries-doped Ce respectively with embodiment 6
3+The ferric phosphate synthetic material of ion.
Respectively with the synthetic material of above-mentioned gained and embodiment 6 at Fe: Ce
3+: the P mol ratio is respectively a kind of anode material for lithium-ion batteries-doped Ce of gained under 0.96: 0.04: 1 condition
3+The ferric phosphate synthetic material of ion is anodal, is negative pole with the lithium sheet, is assembled into battery, carries out electro-chemical test and charge-discharge test.The charging and discharging curve of gained is seen Fig. 8 respectively.Different as can be seen from Figure 8 Ce
3+The doping of mixing is influential to the capacity of ferric phosphate material.The purpose of ion doping mainly is to change Fe (II) PO
4/ Fe (III) PO
4The charge structure at interface or lattice structure.Doping is too high, can influence the electrochemical reaction current potential of material, and making does not have activity under the charge and discharge platform current potential, thereby has reduced the capacity of material.
Ferric phosphate to the different ions ion doping carries out the XRD test, as shown in Figure 9.As can be seen from Figure 9, the material that is synthesized is the very little ferric phosphate of particle diameter, is rendered as " steamed bun peak " in the drawings.And the change with dopant ion does not change.
Ferric phosphate synthetic material with the different dopant ions of embodiment 1,2,3,5 and 6 gained is a positive pole, with the lithium sheet is negative pole, is assembled into battery, carries out the electrochemical impedance spectroscopy test of electrode, the results are shown in Figure 10, the impedance arc among Figure 10 is represented electric charge transfger impedance in the electrode charge and discharge.As can be seen from Figure 10 the impedance circular arc is more little, shows that electrochemical reaction is easy more to carry out, and lithium ion embeds-move out impedance in charge and discharge process just more little, and the polarization in the battery charging and discharging is just more little.Also explanation has improved the conductivity and the chemical property of ferric phosphate material by doping vario-property.
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 (5)
1. the ferric phosphate of an anode material for lithium-ion batteries-doped metal ion is characterized in that it is made up of Fe source, P source and doped metal ion;
Fe wherein: the mol ratio of doped metal ion: P is 0.92～0.99: 0.01～0.08: 1; Wherein doped metal ion is Al
3+, Cr
3+, Cu
2+Or Ce
3+
2. the co-precipitation preparation method of the ferric phosphate of a kind of anode material for lithium-ion batteries-doped metal ion as claimed in claim 1 is characterized in that comprising being prepared as follows step:
(1), the mixing of raw material
Phosphorus source, source of iron and doped metal ion are joined dissolving mixing in the container that fills pure water, form phosphorus source, source of iron and doped metal ion raw mix;
Described phosphorus source is the phosphate or the phosphoric acid of solubility; Wherein the phosphate of solubility is (NH
4)
2HPO
4Or NH
4H
2PO
4
Wherein source of iron is carbonate, acetate, nitrate, the oxide of iron or the hydroxide of iron of iron;
Wherein doped metal ion is Al
3+, Cr
3+, Cu
2+Or Ce
3+Soluble-salt or hydroxide or oxide;
Al
3+, Cr
3+, Cu
2+Or Ce
3+Soluble-salt be Al
3+, Cr
3+, Cu
2+Or Ce
3+Nitrate or acetate;
(2), the preparation of the precursor of the ferric phosphate of doped metal ion
Is under 20～100 ℃ with the raw mix of phosphorus, iron and the doped metal ion of step (1) gained in temperature, obtains the precursor of the ferric phosphate of doped metal ion by co-precipitation or sol-gel process;
(3), the preparation of the ferric phosphate of doped metal ion
Ferric phosphate precursor to the doped metal ion of step (2) gained washs, filters, then it is heat-treated, promptly control temperature at 300～600 ℃, sintering is 5 hours in air, sieve after crushed again, promptly form the ferric phosphate of the positive electrode-doped metal ion of lithium ion battery of the present invention.
3. the co-precipitation preparation method of the ferric phosphate of a kind of anode material for lithium-ion batteries-doped metal ion as claimed in claim 2 is characterized in that the phosphorus described in the preparation process (1) is preferably NH
4H
2PO
4Described iron is preferably Fe (NO
3)
3
Described Al
3+, Cr
3+, Cu
2+Or Ce
3+Soluble-salt be Al
3+, Cr
3+, Cu
2+Or Ce
3+Nitrate.
4. the solid phase synthesis preparation method thereof of the ferric phosphate of a kind of anode material for lithium-ion batteries-doped metal ion as claimed in claim 1 comprises being prepared as follows step:
(1), the ball milling of raw material mixes
Phosphorus source, source of iron and doped metal ion are carried out ball milling mix, form phosphorus source, source of iron and doped metal ion raw mix;
Described phosphorus source is ammonium phosphate or diammonium hydrogen phosphate or phosphoric acid;
Wherein source of iron is di-iron trioxide, ferric carbonate or ferric acetate;
Wherein doped metal ion is Al
3+, Cr
3+, Cu
2+Or Ce
3+Salt or hydroxide or oxide; Al
3+, Cr
3+, Cu
2+Or Ce
3+Salt be Al
3+, Cr
3+, Cu
2+Or Ce
3+Carbonate, nitrate or acetate;
(2), the preparation of the ferric phosphate of doped metal ion
To heat-treat by the mixed compound of ball milling in the step (1), promptly control temperature at 300～600 ℃, sintering is 5 hours in air, sieves after crushed again, promptly forms the ferric phosphate of the positive electrode-doped metal ion of lithium ion battery of the present invention.
5. as the solid phase synthesis preparation method thereof of the ferric phosphate of the described a kind of anode material for lithium-ion batteries-doped metal ion of right claim 4, it is characterized in that the phosphorus source described in the preparation process (1) is preferably (NH
4)
2HPO
4
Described source of iron is preferably Fe
2(CO
3)
3
Described Al
3+, Cr
3+, Cu
2+Or Ce
3+Soluble-salt be preferably Al
3+, Cr
3+, Cu
2+Or Ce
3+Nitrate.
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| CN102976302A (en) * | 2012-12-10 | 2013-03-20 | 秦皇岛科维克科技有限公司 | Rare-earth-doped iron phosphate material and preparation method thereof |
| CN103165882A (en) * | 2011-12-15 | 2013-06-19 | 河南科隆集团有限公司 | Preparation method for positive electrode material--lithium iron phosphate |
| CN106129331A (en) * | 2016-08-31 | 2016-11-16 | 四川剑兴锂电池有限公司 | A kind of anode pole piece and the lithium titanate battery containing this anode pole piece |
| CN106842059A (en) * | 2017-03-07 | 2017-06-13 | 河海大学常州校区 | Lithium battery both positive and negative polarity electrochemical properties on-line monitoring method based on three electrode measurements |
| CN107308968A (en) * | 2017-07-11 | 2017-11-03 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of Fe2O3 doping indium phosphate photochemical catalyst |
| CN111276693A (en) * | 2020-01-22 | 2020-06-12 | 上海华谊（集团）公司 | Modification method of lithium manganese iron phosphate, modified lithium manganese iron phosphate and application thereof |
| CN112582608A (en) * | 2020-12-10 | 2021-03-30 | 散裂中子源科学中心 | Silicon-doped iron-based polyanion compound and preparation method and application thereof |
| CN115172718A (en) * | 2022-08-01 | 2022-10-11 | 湖北万润新能源科技股份有限公司 | Method for preparing lithium iron manganese phosphate by solid-phase coating method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103165882A (en) * | 2011-12-15 | 2013-06-19 | 河南科隆集团有限公司 | Preparation method for positive electrode material--lithium iron phosphate |
| CN102976302A (en) * | 2012-12-10 | 2013-03-20 | 秦皇岛科维克科技有限公司 | Rare-earth-doped iron phosphate material and preparation method thereof |
| CN102976302B (en) * | 2012-12-10 | 2014-12-24 | 秦皇岛科维克科技有限公司 | Rare-earth-doped iron phosphate material and preparation method thereof |
| CN106129331A (en) * | 2016-08-31 | 2016-11-16 | 四川剑兴锂电池有限公司 | A kind of anode pole piece and the lithium titanate battery containing this anode pole piece |
| CN106842059A (en) * | 2017-03-07 | 2017-06-13 | 河海大学常州校区 | Lithium battery both positive and negative polarity electrochemical properties on-line monitoring method based on three electrode measurements |
| CN107308968A (en) * | 2017-07-11 | 2017-11-03 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of Fe2O3 doping indium phosphate photochemical catalyst |
| CN111276693A (en) * | 2020-01-22 | 2020-06-12 | 上海华谊（集团）公司 | Modification method of lithium manganese iron phosphate, modified lithium manganese iron phosphate and application thereof |
| CN112582608A (en) * | 2020-12-10 | 2021-03-30 | 散裂中子源科学中心 | Silicon-doped iron-based polyanion compound and preparation method and application thereof |
| CN112582608B (en) * | 2020-12-10 | 2021-10-01 | 散裂中子源科学中心 | Silicon-doped iron-based polyanion compound and preparation method and application thereof |
| CN115172718A (en) * | 2022-08-01 | 2022-10-11 | 湖北万润新能源科技股份有限公司 | Method for preparing lithium iron manganese phosphate by solid-phase coating method |
| WO2024027085A1 (en) * | 2022-08-01 | 2024-02-08 | 湖北万润新能源科技股份有限公司 | Method for preparing lithium manganese iron phosphate by solid-phase coating method |
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