CN102502562B - Preparation method of lithium iron phosphate, lithium ion battery and anode material and anode thereof - Google Patents
Preparation method of lithium iron phosphate, lithium ion battery and anode material and anode thereof Download PDFInfo
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Abstract
The invention provides a preparation method of lithium iron phosphate, a lithium ion battery and an anode material and an anode thereof. The preparation method of the lithium iron phosphate comprises the following steps of: uniformly mixing lithium dihydrogen phosphate with an iron source to obtain a mixture material, wherein the molar ratio of lithium to iron in the mixture material is (1-1.02):(0.98-1), and the iron source comprises a bivalent iron source compound, a trivalent inorganic iron source compound and a trivalent organic iron source compound; and preheating the mixture material under the protection of inert gas, and calcining to obtain lithium iron phosphate powder. Due to the adoption of the method, a lithium iron phosphate material of which the particle diameter is distributed in a non-normal way can be further prepared by using the method, the electronic conductivity and lithium ion conducting rate of the material are increased simultaneously, the tap density of the material is increased, the high-rate discharge performance of the material is improved, and the material has high specific volumetric capacity and low Fe2P impurity content.
Description
Technical field
The present invention relates to lithium ion battery field, particularly a kind of preparation method of LiFePO4, lithium ion battery and positive electrode thereof and positive pole.
Background technology
LiFePO4 is mainly used in the positive electrode of lithium ion battery, with traditional lithium ion secondary battery anode material as the LiMn of spinel structure
2o
4liCoO with layer structure
2compare, the raw material source of LiFePO4 is more extensive, and price is also comparatively cheap.In addition, LiFePO4 also has the feature of large, the safe to use and asepsis environment-protecting of discharge capacity, and extremely people pay close attention in recent years.
Solid-phase synthesis is the main synthetic method of LiFePO4, and prior art provides the multiple method of utilizing solid-phase synthesis to prepare LiFePO4, for example: Liu etc. [Journal of Power Sources, 2006,159:717-720] are with Li
2cO
3, FeC
2o
42H
2o, NH
4h
2pO
4, acetylene black is raw material, according to Li: Fe: P mol ratio is 1: 1: 1 mixed material, is incubated 15h after ball milling 24h in the tube furnace of 750 DEG C, has obtained nanoscale LiFePO4/C composite material, and the particle diameter of resulting materials is 100nm.Because grain diameter is less, lithium ion the evolving path is short, and the high rate performance of material gets a promotion.But due to nanometer materials poor processability, high to coating and mixing plant requirement, the prices of raw and semifnished materials are higher in addition, and synthetic material is more expensive, and price is comparatively expensive.
Crowns etc. [high chemical journal, 2007,28:136-139] are with Fe
2o
3for raw material, utilize carbothermic method to prepare LiFePO
4/ C composite material, research shows, the specific discharge capacity of this material of 0.1C multiplying power is 144.8mAh/g.The method can produce strong reducing atmosphere in reduction process, and can utilize the ferric iron compounds such as iron oxide is source of iron, thereby has reduced cost of material.But the standby material particle size of this legal system is generally in micron level, therefore synthetic material material capacity performance and the high rate performance aspect synthetic compared with conventional high-temperature solid phase method is on the low side.
Zhong Meie etc. [Acta PhySico-Chimica Sinica, 2009,25:1504-1510] are with inorganic Fe
2o
3with organic ironic citrate (FeC
6h
5o
75H
2o) for mixing source of iron, utilizing the citrate in ironic citrate is carbon source and reducing agent, has successfully prepared high density LiFePO by solid phase-carbothermic method
4/ C composite material.Material grains is made up of nano particle and micron particles.This method is conducive to improve the coated uniformity of carbon in material, and material high rate performance conservation rate is better, but synthetic LiFePO
4/ C composite material initial discharge poor-performing, this is mainly due in order to ensure reducing atmosphere, the addition of ironic citrate is excessive, causes and in material, has too much Fe
2p impurity produces.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method, lithium ion battery and positive electrode thereof and positive pole of LiFePO4, LiFePO4 prepared by said method to have higher tap density and high rate performance preferably, Fe
2p impurity content is low.
In view of this, the invention provides a kind of preparation method of LiFePO4, comprising:
A), lithium dihydrogen phosphate and source of iron are mixed, obtain mixed material, in described mixed material, the mol ratio of lithium and iron is (1～1.02): (0.98～1); Described source of iron comprises: ferrous iron source compound, trivalent inorganic iron source compound and trivalent Organic Iron source compound;
B), under inert gas shielding, described mixtures of materials is heated to 5h～20h under the condition of 300 DEG C～500 DEG C, cooling, after grinding, obtain precursors;
C), under inert gas shielding, described precursors is calcined to 10h～40h under the condition of 600 DEG C～800 DEG C, cooling, after grinding, obtain iron phosphate powder.
Preferably, described ferrous iron source compound is ferrous oxalate and/or ferrous acetate.
Preferably, described trivalent inorganic iron source compound is iron oxide and/or ferric nitrate.
Preferably, described trivalent Organic Iron source compound is ironic citrate.
Preferably, described ferrous iron source compound.The mol ratio of trivalent inorganic iron source compound and trivalent Organic Iron source compound is (0.2～0.6): (0.16～0.36): (0.08～0.26).
The mode of preferably, mixing described in step a is that high speed ball milling mixes.
The present invention also provides a kind of anode material for lithium-ion batteries, the iron phosphate powder that it is made up of said method.
The present invention also provides a kind of lithium ion cell positive, comprises matrix and the coating material that is placed in matrix surface, and described coating material comprises: above-mentioned anode material for lithium-ion batteries, electric conducting material and binding agent.
The present invention also provides a kind of lithium ion battery, comprises above-mentioned lithium ion cell positive, negative pole, and is arranged on barrier film and electrolyte between described positive pole and negative pole.
The invention provides a kind of preparation method of LiFePO4, the method is taking lithium dihydrogen phosphate as lithium source, taking ferrous iron source compound, trivalent inorganic iron source compound and trivalent Organic Iron source compound as source of iron, adopt high temperature solid-state-carbo-thermal process to prepare LiFePO4.The material particle size forming after on sintering due to varigrained source of iron has impact, therefore the present invention adopts the discrepant above-mentioned mixing source of iron of self particle diameter to be conducive to a step to prepare the LiFePO 4 material of particle diameter Non-Gaussian Distribution, small-particulate materials has more excellent high rate performance, larger particles has advantages of compared with high-tap density, thus in having improved the electronic conductivity and lithium ion conduction speed of material, also improved the tap density of material, not only improve the large multiplying power discharging property of material, but also made material there is higher volume and capacity ratio.
Meanwhile, the introducing of divalence source of iron in preparation method provided by the invention, the amount that makes to mix the inorganic source of iron of trivalent in source of iron reduces, and reduction carbon required in building-up process is reduced, thereby has reduced the addition of the organic source of iron of trivalent, produces excessive Fe after having contained cracking
2p impurity, reduces Fe in material
2the content of P impurity.
Brief description of the drawings
Fig. 1 is the XRD figure of the product prepared of the embodiment of the present invention 1.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The preparation method who the embodiment of the invention discloses a kind of LiFePO4, comprises the steps:
A), lithium source and source of iron are mixed, obtain mixed material, in described mixed material, the mol ratio of lithium and iron is (1～1.02): (0.98～1), and described source of iron comprises: ferrous iron source compound, trivalent inorganic iron source compound and trivalent Organic Iron source compound;
B), under inert gas shielding, described mixed material is heated to 5h～20h under the condition of 300 DEG C～500 DEG C, cooling, after grinding, obtain precursors;
C), under inert gas shielding, described precursors is calcined to 10h～40h under the condition of 600 DEG C～800 DEG C, cooling, after grinding, obtain iron phosphate powder.
In above-mentioned preparation method, step a is the process of prepared product material mixture, the present invention is as the reason of source of iron using the mixture of ferrous iron source compound, trivalent inorganic iron source compound and trivalent Organic Iron source compound: the material particle size that varigrained source of iron forms after on sintering has impact, raw material granularity is less, in sintering process, more easily form and there is the material of smaller particle size, and the difference of different types of source of iron self size is conducive to a step and prepares the iron phosphate powder of different-grain diameter.Ferrous iron source compound particle diameter is little, is also had compared with small particle diameter by its synthetic LiFePO 4 material, and the good rate capability of material easily forms large space but particle diameter is too small in banking process, and the tap density of material is lower; And trivalent inorganic iron source compound particle diameter is larger, raw material pattern is controlled, is conducive to the synthetic LiFePO 4 material having compared with high-tap density; The inorganic source of iron of trivalent is conducive to obtain the LiFePO 4 material of good covering property in sintering process.Therefore, adopt above-mentioned mixing source of iron to there is different particle size distribution intervals for ensureing product, improve the high rate performance that improves material of the tap density of material.
As preferred version, in control source of iron of the present invention, the preferred molar ratio of ferrous iron source compound, trivalent inorganic iron source compound and trivalent Organic Iron source compound example is (0.2～0.6): (0.16～0.36): (0.08～0.26).
Wherein, ferrous iron source compound is preferably ferrous oxalate and/or ferrous acetate.Trivalent inorganic iron source compound is preferably iron oxide and/or ferric nitrate, and it has higher volumes specific energy.Trivalent Organic Iron source compound is preferably ironic citrate.
In above-mentioned material, lithium dihydrogen phosphate as lithium source again as phosphorus source, the present invention selects the reason of lithium dihydrogen phosphate to be: first, select lithium dihydrogen phosphate to reduce the raw material type of required mixing, be conducive to industry control stability, helpful to the stability of the material being synthesized; Secondly, with respect to phosphoric acid such as ammonium di-hydrogen phosphates, it can not produce ammonia, and environmental pollution is little.
In mixtures of materials, the mol ratio of the iron in lithium and the source of iron in lithium source is (1～1.02): (0.98～1), even if lithium slightly carries out suitable excessive processing, this be because: on the one hand, in material, iron content is too high, and lithium content is too low, can cause iron atom to occupy the room of lithium atom, thereby block the one-dimensional movement passage of lithium ion in LiFePO4, cause lithium ion diffusion rate to decline, the specific discharge capacity of material and high rate performance reduce; On the other hand, there is the volatilization problem that is easy in lithium raw material in high-temperature reaction process.The mol ratio of control lithium source of the present invention and source of iron is in above-mentioned scope to ensure material discharging specific capacity and high rate performance for this reason, and it is (1～1.02) that the present invention preferably controls in mixtures of materials the mol ratio of lithium and iron in mixed material: (0.98～0.99).
In step a, for each component in material is mixed, the mode that the present invention preferably adopts high speed ball milling to mix is mixed.More preferably carry out wet-milling using ethanol as dispersant, the addition of ethanol is preferably 1.5～3 times of mixtures of materials weight.A) each raw material is mixed according to step, just obtain mixtures of materials.The mixtures of materials obtaining is proceeded to preliminary treatment according to step b.
Mixtures of materials is carried out pretreated process by step b, and Main Function is by raw material predecomposition, forms the PO that contains with reactivity
4 3-, Li
+, Fe
2+/ Fe
3+with the reaction precursor that decomposes carbon.In this process, can produce the gases such as a large amount of water, carbon dioxide and carbon monoxide, reaction temperature is high, the long abundant decomposition that is conducive to raw material of reaction time, in follow-up sintering process, because the gas producing again tails off, in stove, atmosphere is convenient to control, and contributes to sintering material electrical property out more stable.But reaction temperature is too high, the reaction time is long, not only causes the waste of the energy, and High Temperature Pre is processed easily generation side reaction for a long time simultaneously, thereby the electrical property of sintering stage material is worsened.For this reason, the temperature of this step process of control of the present invention is 300 DEG C～500 DEG C, and be 5h～20h heating time.Heating-up temperature is preferably 320 DEG C～450 DEG C, more preferably 340 DEG C～400 DEG C.Be preferably 8h～15h heating time.
According to step b, mixing of materials is carried out calcining according to step c after the pre-heat treatment.The reaction that calcination process occurs is as follows:
LiH
2PO
4+FeC
2O
4(Fe(C
2H
3O
2)
2)→LiFePO
4+H
2O+CO
2+CO
LiH
2PO
4+Fe
2O
3(Fe(NO
3)
3)+FeC
6H
5O
7→LiFePO
4+H
2O+CO
2+CO+C
The temperature and time of calcining has material impact to the chemical property of product, and reaction temperature is high, and atom activation energy is better, raw material more easily reacts completely and forms the material of high-crystallinity, the degree of crystallinity of material is higher, and grain size is less, and material discharging specific capacity and high rate performance are higher.Under equal conditions, reaction temperature is too high, and material grains is larger, and material discharging high rate performance worsens, and reaction temperature is too low, the crystallization imperfection of material, and material discharging performance worsens.But reaction temperature is too high, the trend of growing up after material crystallization is strong, and in insulating process thereafter, crystal grain is easily grown up.In addition, in course of reaction, material crystallization is improved and grain growth carries out simultaneously, and when the present invention is used for ensureing to be tending towards perfect because of crystal grain crystallization to the control in reaction time, grain growth worsens outstanding to material electrical property.Reaction time is long, and material grains is larger, and the reaction time is too short, material crystallization imperfection.For this reason, the calcining heat of control step c of the present invention is 600 DEG C～800 DEG C, and the time is 10h～40h.Calcining heat is preferably made as 650 DEG C～750 DEG C, and calcination time is preferably 20h～30h.After calcining, calcined product is cooling, grind and just obtain iron phosphate powder.
From such scheme, the present invention is taking lithium dihydrogen phosphate as lithium source, and with ferrous iron source compound, the mixture of trivalent inorganic iron source compound and trivalent Organic Iron source compound is source of iron, adopts high temperature solid-state-carbo-thermal process to prepare LiFePO4.The material particle size forming after on sintering due to varigrained source of iron has impact, therefore the present invention adopts the discrepant above-mentioned mixing source of iron of self particle diameter to be conducive to a step to prepare the LiFePO 4 material of particle diameter Non-Gaussian Distribution, small-particulate materials has more excellent high rate performance, larger particles has advantages of compared with high-tap density, in having improved the electronic conductivity and lithium ion conduction speed of material, also improved the tap density of material, not only improve the large multiplying power discharging property of material, but also made material there is higher volume and capacity ratio.
Meanwhile, the introducing of divalence source of iron in preparation method provided by the invention, the amount that makes to mix the inorganic source of iron of trivalent in source of iron reduces, and reduction carbon required in building-up process is reduced, thereby has reduced the addition of the organic source of iron of trivalent, produces excessive Fe after having contained cracking
2p impurity, reduces Fe in material
2the content of P impurity.
In addition, the present invention also realizes the even mixing of different-grain diameter LiFePO4, has solved the industrial problem that is difficult to mix by the material of each particle diameter in physical mixing processes after synthetic different performance LiFePO4.
The present invention also provides a kind of anode material for lithium-ion batteries, its iron phosphate powder for being prepared by said method.This LiFePO 4 material has higher tap density and high rate performance preferably.
The present invention also provides a kind of lithium ion cell positive, and it comprises: matrix and the coating material that is placed in matrix surface, wherein, coating material comprises: above-mentioned anode material for lithium-ion batteries, electric conducting material and bonding agent.
In above-mentioned positive pole, matrix can adopt material well known to those skilled in the art, as aluminium foil.In coating material, electric conducting material is preferably electrically conductive graphite, and bonding agent can be polytetrafluoroethylene, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate or butadiene-styrene rubber.
Anode of secondary battery provided by the invention can be adopted preparation with the following method:
Above-mentioned positive electrode, electric conducting material, binding agent are dissolved in to 1-METHYLPYRROLIDONE and are pressed in the positive pole of making on matrix after mixing.
Accordingly, the present invention also provides a kind of lithium ion battery, comprising: above-mentioned ion battery positive pole, negative pole, be arranged on barrier film and electrolyte between positive pole and negative pole.This lithium ion battery adopts above-mentioned LiFePO 4 material as positive electrode, because this material has higher tap density and volume and capacity ratio, also makes the electrochemistry of this battery to promote.
For further reason the present invention, below in conjunction with embodiment, the preparation method of LiFePO4 provided by the invention is described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
1,, taking absolute ethyl alcohol as dispersant, 1.02mol lithium dihydrogen phosphate, 0.4mol ferrous oxalate, 0.255mol iron oxide and 0.09mol ironic citrate are mixed through high speed ball mill ball milling;
2, mixed raw material is placed in to tubular heater, passes into nitrogen as protective gas, be warming up to 350 DEG C, constant temperature 10 hours, cooling rear grinding obtains reacting precursor;
3, step 2 gained precursors is put into reactor, is placed in tube furnace, pass into nitrogen as protective gas, be warming up to 700 DEG C, constant temperature 24 hours, cooling with stove after, grind, sieve, gained powder is LiFePO 4 material.
The XRD figure that is illustrated in figure 1 product prepared by the present embodiment, as seen from the figure, LiFePO4 is successfully prepared, and in figure without Fe
2the diffraction maximum of P, illustrates that the method contained Fe thus
2the generation of P.
The particle size distribution of LiFePO 4 material prepared by test the present embodiment, test result is: this LiFePO4 has three interval particle size distribution, is respectively low footpath peak 0.2～0.1um, central diameter peak 0.1～2um, high footpath peak 2～10um.
Embodiment 2
1,, taking absolute ethyl alcohol as dispersant, 1.02mol lithium dihydrogen phosphate, 0.4mol ferrous oxalate, 0.24mol iron oxide and 0.12mol ironic citrate are mixed through high speed ball mill ball milling;
2, mixed raw material is placed in to tube furnace, passes into argon gas as protective gas, be warming up to 250 DEG C, constant temperature 10 hours, cooling, grind after obtain precursors;
3, precursors step 2 being made is put into reactor, is placed in tube furnace, passes into nitrogen as protective gas, is warming up to 800 DEG C, calcining at constant temperature 32 hours, cooling with stove, grind, sieve after gained powder be LiFePO 4 material.
The particle size distribution of LiFePO 4 material prepared by test the present embodiment, test result is: this LiFePO4 has three interval particle size distribution, is respectively low footpath peak 0.2～1um, central diameter peak 1～3um, high footpath peak 3～10um.
Embodiment 3
1,, taking absolute ethyl alcohol as dispersant, 1mol lithium dihydrogen phosphate, 0.2mol ferrous oxalate, 0.36mol iron oxide and 0.08mol ironic citrate are mixed through high speed ball mill ball milling;
2, mixed raw material is placed in to tubular heater, passes into nitrogen as protective gas, be warming up to 400 DEG C, constant temperature 5 hours, cooling rear grinding obtains reacting precursor;
3, step 2 gained precursors is put into reactor, is placed in tube furnace, pass into nitrogen as protective gas, be warming up to 500 DEG C, constant temperature 40 hours, cooling with stove after, grind, the gained powder that sieves is LiFePO 4 material.
The particle size distribution of LiFePO 4 material prepared by test the present embodiment, test result is: this LiFePO4 has three interval particle size distribution, is respectively low footpath peak 0.2～2um, central diameter peak 2～4um, high footpath peak 4～10um.
Embodiment 4
1,, taking absolute ethyl alcohol as dispersant, 1mol lithium dihydrogen phosphate, 0.6mol ferrous acetate, 0.16mol iron oxide and 0.08mol ironic citrate are mixed through high speed ball mill ball milling;
2, mixed raw material is placed in to tubular heater, passes into argon gas as protective gas, be warming up to 300 DEG C, constant temperature 20 hours, cooling rear grinding obtains reacting precursor;
3, step 2 gained precursors is put into reactor, is placed in tube furnace, pass into nitrogen as protective gas, be warming up to 650 DEG C, constant temperature 10 hours, cooling with stove after, grind, the gained powder that sieves is LiFePO 4 material.
The particle size distribution of LiFePO 4 material prepared by test the present embodiment, test result is: this LiFePO4 has three interval particle size distribution, is respectively low footpath peak 0.2～3um, central diameter peak 3～5um, high footpath peak 5～10um.
Embodiment 5
1,, taking absolute ethyl alcohol as dispersant, 1mol lithium dihydrogen phosphate, 0.58mol ferrous oxalate, 0.16mol ferric nitrate and 0.08mol ironic citrate are mixed through high speed ball mill ball milling;
2, mixed raw material is placed in to tubular heater, passes into nitrogen as protective gas, be warming up to 300 DEG C, constant temperature 20 hours, cooling rear grinding obtains reacting precursor;
3, step 2 gained precursors is put into reactor, is placed in tube furnace, pass into nitrogen as protective gas, be warming up to 600 DEG C, constant temperature 12 hours, cooling with stove after, grind, the gained powder that sieves is iron phosphate powder.
The particle size distribution of LiFePO 4 material prepared by test the present embodiment, test result is: this LiFePO4 has three interval particle size distribution, is respectively low footpath peak 0.2～4um, central diameter peak 4～6um, high footpath peak 6～10um.
Embodiment 6
1,, taking absolute ethyl alcohol as dispersant, 1mol lithium dihydrogen phosphate, 0.2mol ferrous oxalate, 0.2mol ferrous acetate, 0.14mol ferric nitrate, 0.1mol iron oxide and 0.26mol ironic citrate, taking ethanol as dispersant, are mixed through high speed ball mill ball milling;
2, mixed raw material is placed in to tubular heater, passes into nitrogen as protective gas, be warming up to 300 DEG C, constant temperature 15 hours, cooling rear grinding obtains reacting precursor;
3, step 2 gained precursors is put into reactor, is placed in tube furnace, pass into nitrogen as protective gas, be warming up to 650 DEG C, constant temperature 14 hours, cooling with stove after, grind, the gained powder that sieves is iron phosphate powder.
The LiFePO 4 material of preparing taking embodiment 1～6 respectively, as positive electrode, is made CR2016 type button experimental cell as follows, and numbering is followed successively by A, B, B, D, E, F:
1, positive electrode is mixed in 8: 1: 1 ratios with electrically conductive graphite super P and binding agent PVDF, be dissolved in 1-METHYLPYRROLIDONE (NMP), the post-drying that stirs, pulverizing, be pressed in aluminium and make positive plate on the net.
2, positive plate step 1 being made is dried 5h in vacuum drying oven at 130 DEG C, dried positive plate, the negative pole of preparing with metal lithium sheet, polypropylene diaphragm and electrolyte are assembled in the glove box that is full of high-purity argon gas, obtained CR2016 type button experimental cell.Wherein in electrolyte, supporting electrolyte is LiPF
6, solvent is that ethylene carbonate (EC) is to mix at 1: 1 with diethyl carbonate (DEC) by volume, the concentration of electrolyte is 1mol/L.
Test above-mentioned 6 CR2016 type button experimental cell 0.1C first discharge specific capacity and tap density, test result is listed in table 1.
Table 1 battery 0.1C first discharge specific capacity and tap density
From the above results, the LiFePO 4 material that adopts the method that the invention provides to prepare has higher tap density and volume and capacity ratio, and Fe2P impurity is few.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a preparation method for LiFePO4, comprising:
A), lithium dihydrogen phosphate and source of iron are mixed, obtain mixture material, in described mixed material, the mol ratio of lithium and iron is (1～1.02): (0.98～1); Described source of iron comprises: ferrous iron source compound, trivalent inorganic iron source compound and trivalent Organic Iron source compound; The mol ratio of described ferrous iron source compound, trivalent inorganic iron source compound and trivalent Organic Iron source compound is (0.2～0.6): (0.16～0.36): (0.08～0.26);
B), under inert gas shielding, described mixture material is heated to 5h～20h under the condition of 300 DEG C～500 DEG C, cooling, after grinding, obtain precursors;
C), under inert gas shielding, described precursors is calcined to 10h～40h under the condition of 600 DEG C～800 DEG C, cooling, after grinding, obtain iron phosphate powder.
2. preparation method according to claim 1, is characterized in that, described ferrous iron source compound is ferrous oxalate and/or ferrous acetate.
3. preparation method according to claim 1, is characterized in that, described trivalent inorganic iron source compound is iron oxide and/or ferric nitrate.
4. preparation method according to claim 1, is characterized in that, described trivalent Organic Iron source compound is ironic citrate.
5. preparation method according to claim 1, is characterized in that, the mode of mixing described in step a is that high speed ball milling mixes.
6. an anode material for lithium-ion batteries, is characterized in that, its iron phosphate powder for being made up of method claimed in claim 1.
7. a lithium ion cell positive, is characterized in that, comprises matrix and the coating material that is placed in matrix surface, and described coating material comprises: anode material for lithium-ion batteries claimed in claim 6, electric conducting material and bonding agent.
8. a lithium ion battery, is characterized in that, comprising: lithium ion cell positive claimed in claim 7, negative pole and be arranged on barrier film and the electrolyte between described positive pole and negative pole.
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| CN102751491B (en) * | 2012-07-03 | 2015-03-18 | 浙江长兴绿色动力能源科技有限公司 | Method for broadening sintering temperature of lithium iron phosphate and preparation method for lithium iron phosphate |
| CN109411707A (en) * | 2018-10-30 | 2019-03-01 | 郭和俊 | A kind of preparation method of LiFePO4 battery core |
| CN111392705B (en) * | 2020-02-25 | 2021-11-12 | 东莞东阳光科研发有限公司 | Preparation method of high-compaction lithium iron phosphate |
| CN113346075A (en) * | 2021-04-29 | 2021-09-03 | 华中科技大学 | Low-temperature-resistant framework composite precursor-based lithium iron phosphate, and preparation method and application thereof |
| CN116081589B (en) * | 2022-10-12 | 2024-03-29 | 北京钠谛科技有限公司 | Lithium-rich lithium iron manganese phosphate material and preparation method thereof |
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| CN1958440A (en) * | 2006-11-24 | 2007-05-09 | 中南大学 | Method for synthesizing Nano level powder of lithium iron phosphate |
| CN102104148A (en) * | 2010-12-31 | 2011-06-22 | 北京中科浩运科技有限公司 | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof |
| CN102148367A (en) * | 2010-02-08 | 2011-08-10 | 江西省金锂科技有限公司 | Method for preparing lithium-ion battery anode material of lithium iron phosphate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958440A (en) * | 2006-11-24 | 2007-05-09 | 中南大学 | Method for synthesizing Nano level powder of lithium iron phosphate |
| CN102148367A (en) * | 2010-02-08 | 2011-08-10 | 江西省金锂科技有限公司 | Method for preparing lithium-ion battery anode material of lithium iron phosphate |
| CN102104148A (en) * | 2010-12-31 | 2011-06-22 | 北京中科浩运科技有限公司 | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof |
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