CN103346317A - Compound doped and cladded lithium ion cell anode material LiFePO4 and preparation method thereof - Google Patents
Compound doped and cladded lithium ion cell anode material LiFePO4 and preparation method thereof Download PDFInfo
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- CN103346317A CN103346317A CN2013102715964A CN201310271596A CN103346317A CN 103346317 A CN103346317 A CN 103346317A CN 2013102715964 A CN2013102715964 A CN 2013102715964A CN 201310271596 A CN201310271596 A CN 201310271596A CN 103346317 A CN103346317 A CN 103346317A
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Abstract
The invention discloses a preparation method of a compound doped and cladded lithium ion cell anode material LiFePO4, comprising the following steps of: mixing, pulping and drying raw materials to obtain a powdery precursor; pre-sintering the powdery precursor; and performing secondary burdening and ball milling on the pre-sintered product, and sintering the obtained mixture to obtain the lithium ion cell anode material LiFePO4, wherein the raw materials comprise a lithium source, an iron source, a phosphorous source and compounds containing doped metal elements which are Nb, Mg, Ti, Mn and Zn. According to the invention, five metal elements are doped in the lithium ion cell anode material LiFePO4, D50 is 1-2mu m, the specific surface area is 16-21.5m<2>/g and the tap density is not less than 1.5g/m<3>. The preparation method is simple and easily-controlled in process and low in production cost. The obtained product is even in component and excellent in physical and chemical properties and electrical property.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation thereof, relate in particular to a kind of doped modified lithium ion battery anode material LiFePO
4And preparation method thereof.
Background technology
Lithium ion battery is since commercialization, and positive electrode is the research focus of field of batteries all the time.A large amount of anode material for lithium-ion batteries that use remain LiCoO at present
2, but owing to Co scarcity of resources on the earth, cause LiCoO
2Expensive.Simultaneously, LiCoO
2Also having obvious defects, mainly is that thermal stability and overcharging resisting performance are relatively poor, and actual specific capacity is on the low side etc.In addition, LiCoO
2Also have hidden danger at secure context, people are seeking other suitable substitution material.In recent years, also developed LiNiO
2, LiMnO
2And LiMn
2O
4Deng positive electrode, but all there is certain defective in these materials.Though nickel is abundanter than cobalt reserves, and is cheap, LiNiO
2The synthesis condition harshness, structural instability easily generates Li
1-yNi
1+yO
2, make part of nickel be arranged in the lithium layer, reduce diffusion rate and the cycle performance of lithium ion.The LiMnO of stratiform
2Because the unsteadiness on the thermodynamics causes its preparation difficulty, and can be converted into spinel structure in the structure of cyclic process laminate, capacity attenuation is very serious.Though the LiMn of spinel structure
2O
4Have characteristics such as higher operating voltage, cheap, environmental friendliness, but in the commercial applications process, LiMn
2O
4Also have following problems to wait to solve: (1) Reversible Cycle capacity is on the low side, is about 115mAh/g; (2) capacitance loss is serious under the high temperature.
From A.K.Padhi in 1997 etc. LiFePO is proposed first
4Can be used as since the anode material for lithium-ion batteries, since this material have low price, nontoxic, Environmental compatibility good, aboundresources, higher specific capacity (theoretical specific capacity 170mAh/g) and higher operating voltage (3.4V, be negative pole with the lithium metal), discharge and recharge to flatten and advantage such as delay, have extended cycle life, high-temperature behavior and security performance are good, LiFePO
4Material has become the focus that battery operated person competitively studies, and is expected to become the leading material of lithium ion battery of future generation.
Yet, because LiFePO
4The restriction of self structure, its poorly conductive and lithium ion diffusion coefficient are low, and poorly conductive is to influence LiFePO
4The main cause of using.Through years of researches, conductivity can be improved about 8 times by mixing, and material specific capacity is near theoretical value, high-rate charge-discharge capability also obtains some improvement simultaneously, has suppressed capacity attenuation to a certain extent.In addition, by dopant activation lattice, improved the lithium ion diffusion coefficient.
The study on the modification of existing LiFePO4 mainly comprises the following aspects:
(1) carbon coats: carbon has good electric conductivity and lower mass density, adds a spot of carbon, can improve the electric conductivity of material, also can reduce the particle diameter yardstick of material in addition.For example Prosni etc. prepares LiFePO
4/ C compound material, its conductivity improve about 1.5 times, and the discharge capacity under 1C reaches 150mAh/g(referring to Huang Kelong, Wang Zhaoxiang, Liu Suqin, lithium ion battery principle and key technology [M], Beijing: Chemical Industry Press, 2008).Tin etc. have contrasted five kinds of LiFePO that carbon source is prepared
4/ C material, find that the carbon doping can effectively improve the conductivity of LiFePO4, but acetylene black, flaky graphite are not good selection, adopt carbon black and glucose and as carbon source, can make the chemical property of product get a greater increase (referring to Nagaura T, Tozawak k.Lithium ion rechargeable battery[J] .Batteries Solar Cells, 1990,9:209-210.).
(2) metal ion mixing: be coated on material surface with carbon and just changed interparticle conductivity, to LiFePO
4The conductivity of granule interior but influences very little.When the size of particle is not enough hour, the charge-discharge performance that obtain big electric current, high power capacity is relatively difficulty, content and the energy density of active principle in the too high easy reduction electrode of carbon content simultaneously still.Therefore, generally improve LiFePO by metal ion mixing
4The conductivity of granule interior.When carrying out metal ion mixing, consider from doping position, can be divided into Li position or Fe position and mix.The identical employing of Liu improved solid phase method has prepared the Li that Mg is mixed in the Li position
0.98Mg
0.02FePO
4Sample, a spot of Mg
2+Be doped with the pattern and the particle diameter that are beneficial to the control product, (referring to Liu Heng, Sun Honggang, Zhou Dali etc., improved solid phase method prepares ferric phosphate lithium cell material [J], Sichuan University's journal, 2004,36 (4): 74-77) to obtain stable LiFePO4 compound.Test result shows: the relative lithium electrode current potential of the charge and discharge platform of lithium ion is about 3.5V in the material, and its initial discharge capacity surpasses 160mAh/g, and capacity only decays 5.5% after 50 charge and discharge cycles, and this shows Mg
2+Doping significantly improved specific energy and cyclical stability.Fe position doped metal ion mainly contains Ti
4+, Mn
2+Deng.Zhong etc. have synthesized LiFePO
4And Li
0.95Fe
0.95Ti
0.05PO
4Positive electrode (referring to Zhong M E, Zhou Z T.Preparation of high tap-density LiFePO
4/ C composite cathode materials by carbothermal reduction method using two kinds of Fe3+precursors materials[J] .Chemistry and physics, 2010,119:428-431.), discover the Ti of doping
4+Occupy Li position and Fe position simultaneously, the initial discharge capacity under the 0.1C multiplying power is up to 158mAh/g, and the voltage platform of 1C is reduced to 3.3V by initial 3.4V, and it is original 70% that specific capacity remains on, with LiFePO
4Compare, titanium doped sample shows better electrochemical performance.A spot of manganese mixes and can reduce the polarization of material, improves the high rate performance of material.This mainly is to have increased LiFePO because manganese mixes
4Unit cell volume, more be conducive to deviating from of lithium, the doping of manganese has caused sintering process to produce crystal structure defects in addition, improved the electron conduction of material, thereby make the high rate performance of material have clear improvement (referring to Padhi A K, Nanjundaswamy K S, Goodenough J B.Phospho-olivines as Positive electrode Mat erials for Rechargeable Lithium Batteries[J] .J Electrochem Soc, 1997,144 (4): 1188.).
Yet the doped chemical of report generally all was one or two kind of metallic element in the past, and the metallic element that relates to more than three kinds is seldom arranged, and its cycle performance of the LiFePO4 behind the doping vario-property and the very difficult raising simultaneously of high rate performance, and the raising degree is also relatively limited.In addition, existing doping vario-property technological operation step complexity, the cost height, industrial chemicals such as the organic solvent that uses in the technical process, ammonium salt pollute environment easily, and the feature of environmental protection of technology also remains further to be improved.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, and the composite mixed and cladded type anode material for lithium-ion batteries LiFePO that a kind of technology is simple and easy to control, production cost is low is provided
4The preparation method, the product composition that this preparation method obtains is evenly, physical and chemical performance and electrical property be all good and be easy to suitability for industrialized production.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of composite mixed and cladded type anode material for lithium-ion batteries LiFePO
4The preparation method, may further comprise the steps:
(1) purchase as lithium source, source of iron, the phosphorus source of raw material and contain the doped metallic elements compound, described doping metals comprises Nb, Mg, Ti, Mn and Zn; Raw material is mixed making beating, dry (for example spray drying or static dry), obtain the powdery presoma;
(2) the powdery presoma that step (1) is obtained carries out pre-burning;
(3) product after step (2) pre-burning is carried out second batch and ball-milling treatment (the ball milling time is preferably 0.5～4 hour), carry out spray drying or static dry behind the ball milling again;
(4) compound that obtains after the step (3) is carried out sintering, obtain all good composite mixed and cladded type anode material for lithium-ion batteries LiFePO of physical and chemical performance and electrical property
4
Among the above-mentioned preparation method, lithium hydroxide, lithium dihydrogen phosphate or lithium carbonate are preferably used in described lithium source, and described source of iron is preferably used ferrous oxalate, and described phosphorus source is preferably with phosphoric acid or lithium dihydrogen phosphate; The preferred mol ratio n of described lithium source and source of iron (Li)/n (Fe)=0.98～1.06, the preferred mol ratio n of described phosphorus source and source of iron (P)/n (Fe)=0.98～1.05.
Among the above-mentioned preparation method, preferably, the described doping metals Mg element compound that contains comprises basic magnesium carbonate, magnesium acetate, magnesium hydroxide, in the magnesium oxalate one or more, the described doping metals Ti element compound that contains comprises titanium dioxide, the described doping metals Mn element compound that contains comprises manganese acetate, basic carbonate manganese, in the manganese oxalate one or more, the described doping metals Zn element compound that contains comprises zinc acetate, basic zinc carbonate, in the zinc oxalate one or more, the described doping metals Nb element compound that contains comprises niobium pentaoxide and/or niobium oxalate, the total mole number of all doped metallic elements and phosphorus source, the mol ratio in source of iron or lithium source is 0.001～0.05.
Among the above-mentioned preparation method, described second batch preferably points in the product after the pre-burning and allocates carbon source into, 1%～10% of the product quality of the amount of allocating into of carbon source after by pre-burning.Described carbon source is preferably used one or both in citric acid, sucrose, glucose, carbon black, the soluble starch.
Among the above-mentioned preparation method, the process conditions of pre-burning preferably are controlled to be in the described step (3): 1 ℃/min of programming rate～10 ℃/min, and 400 ℃～700 ℃ of holding temperatures, temperature retention time 1～20 hour is cooled off naturally with stove.
Among the above-mentioned preparation method, the process conditions of sintering preferably are controlled to be in the described step (5): 1 ℃/min of programming rate～10 ℃/min, and 600 ℃～900 ℃ of holding temperatures, temperature retention time 1～20 hour is cooled off naturally with stove.
Among the above-mentioned preparation method, the mixing pulping process in the described step (1) preferably refers to: described phosphorus source is placed a container, add under continuous stirring condition and contain the doped metallic elements compound; Continue mechanical agitation then, and the adding of lithium source is wherein got slip, adopt deionized water cooling slip, when slurry temperature drops to 30 ℃～60 ℃, pour vertical mill into, and add source of iron, lasting Vertical Mill 0.5h～4h; Collect slip.
As a total technical conceive, the anode material for lithium-ion batteries LiFePO that the present invention also provides a kind of above-mentioned preparation method to make
4, described anode material for lithium-ion batteries LiFePO
4Middle mixing and doping has Nb, Mg, Ti, Mn and five kinds of metallic elements of Zn, described anode material for lithium-ion batteries LiFePO
4D
50In 1 μ m～2 μ m, specific area at 16m
2/ g～21.5m
2/ g, tap density 〉=1.5g/cm
3
Technique scheme of the present invention is based on our following research institute and proposes: improving LiFePO when metallic element mixes separately
4The chemical property aspect all tool have certain effect; For example, Mg
2+Doping can improve LiFePO
4The intrinsic ionic mobility, reduce the lattice mismatch of two-phase compound in the charge and discharge process, improve transformation rate and high power charging-discharging capacity; Ti
4+Mix and can suppress LiFePO effectively
4The reunion of particle makes the material refinement, increases substantially LiFePO simultaneously
4Chemical property, particularly big multiplying power under cycle performance; And Nb
5+As lithium position doped metal ion, can provide more passage for the diffusive migration of lithium ion; Mn
2+Doping can make Mn
2+Metal ion infiltrates LiFePO
4Granule interior forms lattice defect, is conducive to Li
+Movement, capacity and cycle performance are promoted; And Zn
2+Doping make LiFePO
4The electric charge transfger impedance reduces, and reversibility strengthens, and improves initial capacity and the cycle performance of material.What we were more deep studies show that, after mixing above five kinds of metallic elements and carbon simultaneously and coating acting in conjunction, can make crystals produce special crystal structure defects, improves LiFePO effectively
4The electronic conductivity of/C composite material is conducive to the quick transmission of lithium ion, and the starting voltage that has reduced the material charge and discharge platform is poor, has reduced the electrode polarization of positive electrode, has increased substantially large current discharging capability and the cycle performance of positive electrode of the present invention.
Compared with prior art, the invention has the advantages that:
(1) the present invention is simultaneously at Li position and Fe position doping Nb, Mg, Ti, Mn and five kinds of metallic elements of Zn, take full advantage of the cooperative effect of Nb, Mg, Ti, Mn and five kinds of doped chemicals of Zn, improve cycle performance and the high rate performance of material greatly, obtained all good anode material for lithium-ion batteries LiFePO of physical and chemical performance and electrical property
4
(2) the present invention adopts water as the batch mixing medium, has avoided the use of organic solvent, reduces cost, and reduces operating risk.
(3) the present invention has kept the uniformity of the synthetic presoma of wet chemical method, and chemical property is good.
(4) the present invention has increased process of lapping between pre-burning and sintering process, has improved the tap density of material.
(5) the present invention does not adopt ammonium salt as raw material, has avoided the generation of ammonia in the roasting process, and whole technical process does not have the generation of other three wastes, environmental friendliness simultaneously.
To sum up, preparation method of the present invention has characteristics such as technology is simple and easy to control, production cost is low, and product composition evenly, physical and chemical performance and electrical property be all good, is easy to suitability for industrialized production.
Description of drawings
The SEM photo of the product that Fig. 1 prepares for the method for the embodiment of the invention 1.
The SEM photo of the product that Fig. 2 prepares for the method for the embodiment of the invention 2.
The SEM photo of the product that Fig. 3 prepares for the method for the embodiment of the invention 3.
The SEM photo of the product that Fig. 4 prepares for the method for the embodiment of the invention 4.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment the present invention is further described, but protection range not thereby limiting the invention.
Embodiment 1:
A kind of composite mixed and cladded type anode material for lithium-ion batteries LiFePO of the present invention as shown in Figure 1
4The preparation method, may further comprise the steps:
(1) raw material is purchased: purchase as lithium hydroxide, ferrous oxalate, the phosphoric acid of raw material and contain the doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Contain the doped metallic elements compound and refer to basic magnesium carbonate, titanium dioxide, manganese acetate, zinc acetate and niobium oxalate; According to Li
0.95Nb
0.01Fe
0.968Mg
0.01Ti
0.006Mn
0.006Zn
0.004PO
4Molecular formula prepare burden.Consider the scaling loss in lithium source and phosphorus source in the sintering process, it is a spot of more than needed to need lithium source and phosphorus source to have, so the mol ratio n of lithium source and source of iron (Li)/n (Fe)=1.04, and the mol ratio n of phosphorus source and source of iron (P)/n (Fe) is about 1.03;
(2) mix making beating: the phosphorus source is placed a container, under continuous stirring condition, add and contain the doped metallic elements compound; Continue mechanical agitation then, and the adding of lithium source is wherein got slip, adopt deionized water cooling slip, when slurry temperature drops to 50 ℃, pour vertical mill into, and add source of iron, lasting Vertical Mill 2h; Collect slip; Carry out spray drying, obtain the powdery presoma;
(3) pre-burning: the powdery presoma that step (2) is obtained carries out pre-burning, and the pre-burning system is: 3 ℃/min of programming rate, and 650 ℃ of holding temperatures, temperature retention time 6 hours is cooled off naturally with stove;
(4) second batch: the product after step (3) pre-burning is carried out second batch and ball-milling treatment, second batch is to allocate carbon source (selecting glucose for use as carbon source) in the product that points to after the pre-burning, 5% of the product quality of the amount of allocating into of carbon source after by pre-burning, after the adding carbon source compound is carried out the ball-milling treatment of 2h, carry out spray drying afterwards;
(5) compound that obtains after the step (4) is carried out sintering, the process conditions of sintering are controlled to be: 3 ℃/min of programming rate, 760 ℃ of holding temperatures, temperature retention time 16 hours, naturally cool off with stove, obtain all good composite mixed and cladded type anode material for lithium-ion batteries LiFePO of physical and chemical performance and electrical property
4
Embodiment 2:
A kind of composite mixed and cladded type anode material for lithium-ion batteries LiFePO of the present invention as shown in Figure 2
4The preparation method, may further comprise the steps:
(1) raw material is purchased: purchase as lithium hydroxide, ferrous oxalate, the phosphoric acid of raw material and contain the doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Contain the doped metallic elements compound and refer to basic magnesium carbonate, titanium dioxide, manganese acetate, zinc acetate and niobium oxalate; According to Li
0.99Nb
0.01Fe
0.984Mg
0.01Ti
0.006Mn
0.006Zn
0.004PO
4Molecular formula prepare burden, consider the scaling loss in lithium source and phosphorus source in the sintering process, the mol ratio n of lithium source and source of iron (Li)/n (Fe) is about 1.04, the mol ratio n of phosphorus source and source of iron (P)/n (Fe) is about 1.03;
(2) mix making beating: the phosphorus source is placed a container, under continuous stirring condition, add and contain the doped metallic elements compound; Continue mechanical agitation then, and the adding of lithium source is wherein got slip, adopt deionized water cooling slip, when slurry temperature drops to 40 ℃, pour vertical mill into, and add source of iron, lasting Vertical Mill 1.5h; Collect slip; Carry out spray drying, obtain the powdery presoma;
(3) pre-burning: the powdery presoma that step (2) is obtained carries out pre-burning, and the pre-burning system is: 2 ℃/min of programming rate, and 640 ℃ of holding temperatures, temperature retention time 6 hours is cooled off naturally with stove;
(4) second batch: the product after step (3) pre-burning is carried out second batch and ball-milling treatment, second batch is to allocate carbon source (selecting glucose for use as carbon source) in the product that points to after the pre-burning, 5% of the product quality of the amount of allocating into of carbon source after by pre-burning, after the adding carbon source compound is carried out the ball-milling treatment of 2.5h, carry out spray drying afterwards;
(5) compound that obtains after the step (4) is carried out sintering, the process conditions of sintering are controlled to be: 2 ℃/min of programming rate, 750 ℃ of holding temperatures, temperature retention time 15 hours, naturally cool off with stove, obtain all good composite mixed and cladded type anode material for lithium-ion batteries LiFePO of physical and chemical performance and electrical property
4
Embodiment 3:
A kind of composite mixed and cladded type anode material for lithium-ion batteries LiFePO of the present invention as shown in Figure 3
4The preparation method, may further comprise the steps:
(1) raw material is purchased: purchase as lithium hydroxide, ferrous oxalate, the phosphoric acid of raw material and contain the doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Contain the doped metallic elements compound and refer to basic magnesium carbonate, titanium dioxide, manganese acetate, zinc acetate and niobium pentaoxide; According to Li
0.984Nb
0.01Ti
0.006Fe
0.98Mg
0.01Mn
0.006Zn
0.004PO
4Molecular formula prepare burden, consider the scaling loss in lithium source and phosphorus source in the sintering process, the mol ratio n of lithium source and source of iron (Li)/n (Fe) is about 1.04, the mol ratio n of phosphorus source and source of iron (P)/n (Fe) is about 1.03;
(2) mix making beating: the phosphorus source is placed a container, under continuous stirring condition, add and contain the doped metallic elements compound; Continue mechanical agitation then, and the adding of lithium source is wherein got slip, adopt deionized water cooling slip, when slurry temperature drops to 45 ℃, pour vertical mill into, and add source of iron, lasting Vertical Mill 2.5h; Collect slip; Carry out spray drying, obtain the powdery presoma;
(3) pre-burning: the powdery presoma that step (2) is obtained carries out pre-burning, and the pre-burning system is: 3 ℃/min of programming rate, and 660 ℃ of holding temperatures, temperature retention time 6.5 hours is cooled off naturally with stove;
(4) second batch: the product after step (3) pre-burning is carried out second batch and ball-milling treatment, second batch is to allocate carbon source (selecting glucose for use as carbon source) in the product that points to after the pre-burning, 5% of the product quality of the amount of allocating into of carbon source after by pre-burning, after the adding carbon source compound is carried out the ball-milling treatment of 1.5h, carry out spray drying afterwards;
(5) compound that obtains after the step (4) is carried out sintering, the process conditions of sintering are controlled to be: 3 ℃/min of programming rate, 770 ℃ of holding temperatures, temperature retention time 18 hours, naturally cool off with stove, obtain all good composite mixed and cladded type anode material for lithium-ion batteries LiFePO of physical and chemical performance and electrical property
4
Embodiment 4:
A kind of composite mixed and cladded type anode material for lithium-ion batteries LiFePO of the present invention as shown in Figure 4
4The preparation method, may further comprise the steps:
(1) raw material is purchased: purchase as lithium dihydrogen phosphate, the ferrous oxalate of raw material and contain the doped metallic elements compound, doping metals comprises Nb, Mg, Ti, Mn and Zn; Contain the doped metallic elements compound and refer to magnesium oxalate, titanium dioxide, manganese oxalate, zinc oxalate and niobium oxalate; According to Li
0.95Nb
0.01Fe
0.967Mg
0.016Ti
0.004Mn
0.005Zn
0.004PO
4Molecular formula prepare burden, consider the scaling loss in lithium source and phosphorus source in the sintering process, the mol ratio n of lithium source and source of iron (Li)/n (Fe) is about 1.02, the mol ratio n of phosphorus source and source of iron (P)/n (Fe) is about 1.04;
(2) mix making beating: the phosphorus source is placed a container, under continuous stirring condition, add and contain the doped metallic elements compound; Continue mechanical agitation then, and the adding of lithium source is wherein got slip, adopt deionized water cooling slip, when slurry temperature drops to 50 ℃, pour vertical mill into, and add source of iron, lasting Vertical Mill 2h; Collect slip; Carry out spray drying, obtain the powdery presoma;
(3) pre-burning: the powdery presoma that step (2) is obtained carries out pre-burning, and the pre-burning system is: 4 ℃/min of programming rate, and 670 ℃ of holding temperatures, temperature retention time 7 hours is cooled off naturally with stove;
(4) second batch: the product after step (3) pre-burning is carried out second batch and ball-milling treatment, second batch is to allocate carbon source (selecting glucose for use as carbon source) in the product that points to after the pre-burning, 5% of the product quality of the amount of allocating into of carbon source after by pre-burning, after the adding carbon source compound is carried out the ball-milling treatment of 2h, carry out spray drying afterwards;
(5) compound that obtains after the step (4) is carried out sintering, the process conditions of sintering are controlled to be: 4 ℃/min of programming rate, 780 ℃ of holding temperatures, temperature retention time 15 hours, naturally cool off with stove, obtain all good composite mixed and cladded type anode material for lithium-ion batteries LiFePO of physical and chemical performance and electrical property
4
Granularity and the specific surface of the product that the above embodiment of the present invention 1～4 makes are as shown in table 1 below, and the electric performance test result is as shown in table 2 below.
The granularity of the product that table 1: embodiment 1～4 makes and specific surface
The electric performance test result of the product that table 2: embodiment 1～4 makes
Claims (9)
1. composite mixed and cladded type anode material for lithium-ion batteries LiFePO
4The preparation method, may further comprise the steps:
(1) purchase as lithium source, source of iron, the phosphorus source of raw material and contain the doped metallic elements compound, described doping metals comprises Nb, Mg, Ti, Mn and Zn; Raw material is mixed making beating, drying, obtain the powdery presoma;
(2) the powdery presoma that step (1) is obtained carries out pre-burning;
(3) product after step (2) pre-burning is carried out second batch and ball-milling treatment;
(4) compound that obtains after the step (3) is carried out sintering, obtain anode material for lithium-ion batteries LiFePO
4
2. preparation method according to claim 1, it is characterized in that: described lithium source is selected lithium hydroxide, lithium dihydrogen phosphate or lithium carbonate for use, and described source of iron is selected ferrous oxalate for use, and described phosphorus source is selected phosphoric acid or lithium dihydrogen phosphate for use; The mol ratio n of described lithium source and source of iron (Li)/n (Fe)=0.98～1.06, the mol ratio n of described phosphorus source and source of iron (P)/n (Fe)=0.98～1.05.
3. preparation method according to claim 1, it is characterized in that: the described doping metals Mg element compound that contains comprises basic magnesium carbonate, magnesium acetate, magnesium hydroxide, in the magnesium oxalate one or more, the described doping metals Ti element compound that contains comprises titanium dioxide, the described doping metals Mn element compound that contains comprises manganese acetate, basic carbonate manganese, in the manganese oxalate one or more, the described doping metals Zn element compound that contains comprises zinc acetate, basic zinc carbonate, in the zinc oxalate one or more, the described doping metals Nb element compound that contains comprises niobium pentaoxide and/or niobium oxalate, the total mole number of all doped metallic elements and phosphorus source, the mol ratio in source of iron or lithium source is 0.001～0.05.
4. preparation method according to claim 1 is characterized in that: described second batch is to allocate carbon source in the product that points to after the pre-burning, and the amount of allocating into of carbon source is by 1%～10% of the pre-burning product quality.
5. preparation method according to claim 4, it is characterized in that: described carbon source is selected one or both in citric acid, sucrose, glucose, carbon black, the soluble starch for use.
6. preparation method according to claim 1 is characterized in that, the process conditions of pre-burning are controlled to be in the described step (2): 1 ℃/min of programming rate～10 ℃/min, and 400 ℃～700 ℃ of holding temperatures, temperature retention time 1～20 hour is cooled off naturally with stove.
7. preparation method according to claim 1 is characterized in that, the process conditions of sintering are controlled to be in the described step (4): 1 ℃/min of programming rate～10 ℃/min, and 600 ℃～900 ℃ of holding temperatures, temperature retention time 1～20 hour is cooled off naturally with stove.
8. preparation method according to claim 1 is characterized in that, the mixing pulping process in the described step (1) refers to: described phosphorus source is placed a container, add under continuous stirring condition and contain the doped metallic elements compound; Continue mechanical agitation then, and the adding of lithium source is wherein got slip, adopt deionized water cooling slip, when slurry temperature drops to 30 ℃～60 ℃, pour vertical mill into, and add source of iron, lasting Vertical Mill 0.5h～4h; Collect slip.
9. one kind as the preparation method makes as described in each in the claim 1～8 anode material for lithium-ion batteries LiFePO
4, it is characterized in that: described anode material for lithium-ion batteries LiFePO
4Middle mixing and doping has Nb, Mg, Ti, Mn and five kinds of metallic elements of Zn, described anode material for lithium-ion batteries LiFePO
4D
50In 1 μ m～2 μ m, specific area at 16m
2/ g～21.5m
2/ g, tap density 〉=1.5g/cm
3
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| CN103515601A (en) * | 2013-10-28 | 2014-01-15 | 金瑞新材料科技股份有限公司 | Positive pole material LiFePO4 for lithium ion battery and preparation method thereof |
| CN103531794A (en) * | 2013-10-28 | 2014-01-22 | 金瑞新材料科技股份有限公司 | Lithium ion battery positive material lithium ferrous phosphate and preparation method |
| CN103972487A (en) * | 2014-05-16 | 2014-08-06 | 厦门钨业股份有限公司 | Multi-component composite oxide material and industrial preparation method thereof |
| CN108400330A (en) * | 2018-03-08 | 2018-08-14 | 蒋央芳 | A kind of preparation method of carbon doping phosphoric acid manganese (III) |
| CN110770165A (en) * | 2017-02-01 | 2020-02-07 | 国家科学研究中心 | Liquid process for preparing vanadium phosphate-carbon composites |
| CN111201650A (en) * | 2017-11-27 | 2020-05-26 | 庄信万丰股份有限公司 | Cathode material |
| CN112340720A (en) * | 2019-08-06 | 2021-02-09 | 湖南师范大学 | Zinc ion battery anode material based on doped zinc manganese phosphate structure and synthetic method thereof |
| CN113148969A (en) * | 2021-04-08 | 2021-07-23 | 江苏力泰锂能科技有限公司 | Doped lithium iron manganese phosphate-carbon composite material and preparation method thereof |
| WO2023179046A1 (en) * | 2022-03-22 | 2023-09-28 | 宜昌邦普循环科技有限公司 | Preparation method for lithium iron phosphate/carbon composite material and use thereof |
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| CN103531794A (en) * | 2013-10-28 | 2014-01-22 | 金瑞新材料科技股份有限公司 | Lithium ion battery positive material lithium ferrous phosphate and preparation method |
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| CN103972487A (en) * | 2014-05-16 | 2014-08-06 | 厦门钨业股份有限公司 | Multi-component composite oxide material and industrial preparation method thereof |
| CN103972487B (en) * | 2014-05-16 | 2016-08-24 | 厦门钨业股份有限公司 | A kind of multicomponent composite oxide material and industrial production process thereof |
| CN110770165A (en) * | 2017-02-01 | 2020-02-07 | 国家科学研究中心 | Liquid process for preparing vanadium phosphate-carbon composites |
| CN111201650A (en) * | 2017-11-27 | 2020-05-26 | 庄信万丰股份有限公司 | Cathode material |
| CN108400330A (en) * | 2018-03-08 | 2018-08-14 | 蒋央芳 | A kind of preparation method of carbon doping phosphoric acid manganese (III) |
| CN108400330B (en) * | 2018-03-08 | 2020-07-14 | 蒋央芳 | Preparation method of carbon-doped manganese (III) phosphate |
| CN112340720A (en) * | 2019-08-06 | 2021-02-09 | 湖南师范大学 | Zinc ion battery anode material based on doped zinc manganese phosphate structure and synthetic method thereof |
| CN113148969A (en) * | 2021-04-08 | 2021-07-23 | 江苏力泰锂能科技有限公司 | Doped lithium iron manganese phosphate-carbon composite material and preparation method thereof |
| WO2023179046A1 (en) * | 2022-03-22 | 2023-09-28 | 宜昌邦普循环科技有限公司 | Preparation method for lithium iron phosphate/carbon composite material and use thereof |
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