CN102502562A - 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 the lithium ion battery field, particularly a kind of method preparing phosphate iron lithium, lithium ion battery and positive electrode material and positive pole.
Background technology
Iron lithium phosphate is mainly used in the positive electrode material of lithium ion battery, with the traditional lithium ion secondary battery anode material such as the LiMn of spinel structure
2O
4LiCoO with laminate structure
2Compare, the former material source of iron lithium phosphate is more extensive, and price is also comparatively cheap.In addition, iron lithium phosphate also has the characteristics of big, the safe to use and asepsis environment-protecting of loading capacity, and extremely people pay close attention in recent years.
Solid-phase synthesis is the main compound method of iron lithium phosphate, and prior art provides the multiple method of utilizing solid-phase synthesis to prepare iron lithium phosphate, and 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: the P mol ratio is 1: 1: 1 mixing raw material, in 750 ℃ tube furnace, is incubated 15h behind the ball milling 24h, has obtained nano level LiFePO4/C matrix material, and the particle diameter of gained material is 100nm.Because grain diameter is less, the lithium ion the evolving path is short, and the high rate performance of material gets a promotion.But because the nanometer materials poor processability requires height to coating and whipping device, the prices of raw and semifnished materials are higher in addition, and the synthetic material is more expensive, and price is comparatively expensive.
Crowns etc. [high chemical journal, 2007,28:136-139] are with Fe
2O
3Be raw material, utilize carbothermic method to prepare LiFePO
4/ C matrix material, research show that the specific discharge capacity of this material of 0.1C multiplying power is 144.8mAh/g.This method can produce the intensive reducing atmosphere in reduction process, can utilize ferric iron compounds such as red stone to be source of iron, thereby reduce raw materials cost.But the material particle size of this method preparation is generally in micron level, so the synthetic material is on the low side than performance of conventional high-temperature solid phase method synthetic material capacity and high rate performance aspect.
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, utilize the citrate in the ironic citrate to be carbon source and reductive agent, successfully prepared high-density LiFePO through solid phase-carbothermic method
4/ C matrix material.Material grains is made up of nano particle and micron particle.This method helps improving carbon cladding uniformity in the material, and material high rate performance conservation rate is better, but synthetic LiFePO
4/ C matrix material initial discharge poor-performing, this mainly is that causing has too much Fe in the material because in order to guarantee reducing atmosphere, the add-on of ironic citrate is excessive
2P impurity produces.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of method preparing phosphate iron lithium, lithium ion battery and positive electrode material thereof and positive pole, and the iron lithium phosphate of method for preparing has higher tap density and more excellent high rate performance, Fe
2The P foreign matter content is low.
In view of this, the present invention provides a kind of method preparing phosphate iron lithium, comprising:
A), monometallic and source of iron are mixed, obtain mixture, the mol ratio of lithium and iron is (1～1.02) in the said mixture: (0.98～1); Said source of iron comprises: ferrous iron source compound, trivalent inorganic iron source compound and the organic Fe source compound of trivalent;
B), under protection of inert gas, said mixtures of materials is heated 5h～20h under 300 ℃～500 ℃ condition, the cooling, obtain the reaction precursor body after the grinding;
C), under protection of inert gas, said reaction precursor body is calcined 10h～40h under 600 ℃～800 ℃ condition, the cooling, obtain iron phosphate powder after the grinding.
Preferably, said ferrous iron source compound is Ferrox and/or Iron diacetate.
Preferably, said trivalent inorganic iron source compound is red stone and/or iron nitrate.
Preferably, the organic Fe source compound of said trivalent is an ironic citrate.
Preferably, said ferrous iron source compound.The mol ratio of trivalent inorganic iron source compound and the organic Fe source compound of trivalent is (0.2～0.6): (0.16～0.36): (0.08～0.26).
Preferably, blended mode described in the step a is the high speed ball mill mixing.
The present invention also provides a kind of anode material for lithium-ion batteries, the iron phosphate powder that it is processed by aforesaid method.
The present invention also provides a kind of lithium ion cell positive, comprises matrix and the coating material that places matrix surface, and said coating material comprises: above-mentioned anode material for lithium-ion batteries, electro-conductive material and sticker.
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 electrolytic solution between said positive pole and the negative pole.
The present invention provides a kind of method preparing phosphate iron lithium; This method is to be the lithium source with the monometallic; With ferrous iron source compound, trivalent inorganic iron source compound and the organic Fe source compound of trivalent is source of iron, adopts high temperature solid-state-carbo-thermal process to prepare iron lithium phosphate.Because the material particle size that varigrained source of iron forms after to sintering is influential; Therefore the present invention adopts the discrepant above-mentioned mixing source of iron of self particle diameter to help one and goes on foot the LiFePO 4 material of preparing the particle diameter skewed distribution; Small-particulate materials has more excellent high rate performance; Larger particles has the advantage than high tap density, in electronic conductivity that has improved material and lithium ion conduction speed, has also improved the tap density of material thus; Not only improved the big multiplying power discharging property of material, but also made material have higher volume and capacity ratio.
Simultaneously, the introducing of divalence source of iron among the preparation method provided by the invention reduces the amount of mixing the inorganic source of iron of trivalent in the source of iron, makes that required reduction carbon reduces in the building-up process, thereby has reduced the add-on of the organic source of iron of trivalent, produces excessive Fe after having contained cracking
2P impurity reduces Fe in the material
2The content of P impurity.
Description of drawings
Fig. 1 is the XRD figure of the product of the embodiment of the invention 1 preparation.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of method preparing phosphate iron lithium, comprise the steps:
A), lithium source and source of iron are mixed, obtain mixture, the mol ratio of lithium and iron is (1～1.02) in the said mixture: (0.98～1), and said source of iron comprises: ferrous iron source compound, trivalent inorganic iron source compound and the organic Fe source compound of trivalent;
B), under protection of inert gas, said mixture is heated 5h～20h under 300 ℃～500 ℃ condition, the cooling, obtain the reaction precursor body after the grinding;
C), under protection of inert gas, said reaction precursor body is calcined 10h～40h under 600 ℃～800 ℃ condition, the cooling, obtain iron phosphate powder after the grinding.
Among the above-mentioned preparation method; Step a is the process of prepared product material mixture; The present invention is with the mixture of ferrous iron source compound, trivalent inorganic iron source compound and the organic Fe source compound of the trivalent reason as source of iron: the material particle size that varigrained source of iron forms after to sintering is influential; Raw material granularity is more little, and easier formation has the material than small grain size in the sintering process, and the difference of different types of source of iron self size helps a step and prepares the iron phosphate powder of different-grain diameter.Ferrous iron source compound particle diameter is little, also has than small particle size by its synthetic LiFePO 4 material, and the good rate capability of material, but too small in banking process, being prone to of particle diameter forms big space, and the tap density of material is lower; And trivalent inorganic iron source compound particle diameter is bigger, and the raw material pattern is controlled, helps the synthetic LiFePO 4 material than high tap density that has; The inorganic source of iron of trivalent helps obtaining the LiFePO 4 material of good covering property in sintering process.Therefore, it is interval to adopt above-mentioned mixing source of iron to be used to guarantee that product has different size-grade distribution, improves the high rate performance that improves material of the tap density of material.
As preferred version, the preferred molar ratio example that the present invention controls ferrous iron source compound in the source of iron, trivalent inorganic iron source compound and the organic Fe source compound of trivalent is (0.2～0.6): (0.16～0.36): (0.08～0.26).
Wherein, the ferrous iron source compound is preferably Ferrox and/or Iron diacetate.Trivalent inorganic iron source compound is preferably red stone and/or iron nitrate, and it has the higher volumes specific energy.The organic Fe source compound of trivalent is preferably ironic citrate.
In the above-mentioned material; Monometallic promptly as the lithium source again as the phosphorus source, the present invention selects the reason of monometallic to be: at first, select for use monometallic to reduce required raw materials mixed kind; Help industry control stability, helpful to the stability of the material that is synthesized; Secondly, with respect to phosphoric acid such as ammonium di-hydrogen phosphates, it can not produce ammonia, and environmental pollution is little.
In the mixtures of materials, the lithium in lithium source and the mol ratio of the iron in the source of iron are (1～1.02): (0.98～1), even lithium carries out suitable excessive processing slightly; This be because: on the one hand, iron level is too high in the material, and lithium content is low excessively; Can cause iron atom to occupy the room of lithium atom; Thereby block the one dimension moving passage of lithium ion in iron lithium phosphate, cause the lithium ion rate of diffusion to descend, the specific discharge capacity of material and high rate performance reduce; On the other hand, there is the volatilization problem that is easy in the lithium raw material in high-temperature reaction process.Guaranteeing material discharging specific storage and high rate performance, the present invention controls preferably in the mixtures of materials that the mol ratio of lithium and iron is (1～1.02) in the mixture to the present invention's mol ratio of controlling lithium source and source of iron: (0.98～0.99) in above-mentioned scope for this reason.
Among the step a, each component mixes in the material in order to make, and the present invention preferably adopts high speed ball milling blended mode to mix.More preferably carry out wet-milling with ethanol as dispersion agent, the alcoholic acid add-on is preferably 1.5～3 times of mixtures of materials weight.According to step a) each raw material is mixed, just obtain mixtures of materials.The mixtures of materials that obtains is proceeded pre-treatment according to step b.
Step b carries out pretreated process with mixtures of materials, and main effect is with raw material predecomposition, forms the PO that contains with reactive behavior
4 3-, Li
+, Fe
2+/ Fe
3+With the reaction precursor that decomposes carbon.Can produce a large amount of gases such as water, carbonic acid gas and carbon monoxide in this process; Temperature of reaction is high; Long reaction time helps the abundant decomposition of raw material, in the follow-up sintering process, because the gas that produces again tails off; Atmosphere is convenient to control in the stove, and the material electrical property that helps sintering to come out is more stable.But temperature of reaction is too high, and the reaction times is long, not only causes the waste of the energy, and the high temperature pre-treatment is prone to side reaction takes place for a long time simultaneously, thereby makes the electrical property of sintering stage material worsen.For this reason, the temperature that the present invention controls this step process is 300 ℃～500 ℃, and be 5h～20h heat-up time.Heating temperature is preferably 320 ℃～450 ℃, more preferably 340 ℃～400 ℃.Be preferably 8h～15h heat-up time.
According to step b mixing of materials is carried out calcining according to step c after the thermal pretreatment.The reaction that calcination process takes place is following:
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 incinerating temperature and time has material impact to the chemical property of product, and temperature of reaction is high, and atom activation energy is good more; Raw material more is prone to react completely and forms the material of high-crystallinity; The percent crystallinity of material is high more, and grain fineness number is more little, and material discharging specific storage and high rate performance are high more.Under the equal conditions, temperature of reaction is too high, and material grains is bigger, and the material discharging high rate performance worsens, and reaction temperature is spent low, the crystallization imperfection of material, material discharging mis-behave.But temperature of reaction is too high, and the trend of growing up after the material crystallization is strong, and crystal grain is grown up easily in insulating process thereafter.In addition, in the reaction process, the material crystallization is improved with grain growth and is carried out simultaneously, and grain growth worsened outstanding when the present invention was used to guarantee to be tending towards perfect because of the crystal grain crystallization to the control in reaction times to the material electrical property.Reaction times is long, and material grains is bigger, and the reaction times is too short, material crystallization imperfection.For this reason, the calcining temperature of controlled step c of the present invention is 600 ℃～800 ℃, and the time is 10h～40h.Calcining temperature preferably is made as 650 ℃～750 ℃, and calcination time is preferably 20h～30h.With the calcinate cooling, grind and just obtain iron phosphate powder after the calcining.
Can be known that by such scheme the present invention is the lithium source with the monometallic, with the ferrous iron source compound, the mixture of trivalent inorganic iron source compound and the organic Fe source compound of trivalent is a source of iron, adopts high temperature solid-state-carbo-thermal process to prepare iron lithium phosphate.Because the material particle size that varigrained source of iron forms after to sintering is influential; Therefore the present invention adopts the discrepant above-mentioned mixing source of iron of self particle diameter to help one and goes on foot the LiFePO 4 material of preparing the particle diameter skewed distribution; Small-particulate materials has more excellent high rate performance; Larger particles has the advantage than high tap density, in electronic conductivity that has improved material and lithium ion conduction speed, has also improved the tap density of material; Not only improved the big multiplying power discharging property of material, but also made material have higher volume and capacity ratio.
Simultaneously, the introducing of divalence source of iron among the preparation method provided by the invention reduces the amount of mixing the inorganic source of iron of trivalent in the source of iron, makes that required reduction carbon reduces in the building-up process, thereby has reduced the add-on of the organic source of iron of trivalent, produces excessive Fe after having contained cracking
2P impurity reduces Fe in the material
2The content of P impurity.
In addition, the present invention also realizes the uniform mixing of different-grain diameter iron lithium phosphate, has solved the industrial last problem that is difficult to mix through the material of each particle diameter in the physical mixing processes behind the synthetic different performance iron lithium phosphate.
The present invention also provides a kind of anode material for lithium-ion batteries, and it is the iron phosphate powder by method for preparing.This LiFePO 4 material has higher tap density and more excellent high rate performance.
The present invention also provides a kind of lithium ion cell positive, and it comprises: matrix and the coating material that places matrix surface, wherein, coating material comprises: above-mentioned anode material for lithium-ion batteries, electro-conductive material and caking agent.
Matrix can adopt material well known to those skilled in the art in the above-mentioned positive pole, like aluminium foil.Electro-conductive material is preferably electrically conductive graphite in the coating material, and caking agent can be tetrafluoroethylene, polyvinylidene dichloride, SE, polymethylmethacrylate or styrene-butadiene rubber(SBR).
Anode of secondary battery provided by the invention can adopt following method preparation:
Above-mentioned positive electrode material, electro-conductive material, sticker are dissolved in N-Methyl pyrrolidone and are pressed in the positive pole of processing on the matrix after mixing.
Accordingly, the present invention also provides a kind of lithium ion battery, comprising: above-mentioned ionization cell positive pole, negative pole, be arranged on barrier film and electrolytic solution between positive pole and the negative pole.This lithium ion battery adopts above-mentioned LiFePO 4 material as positive electrode material, 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 method preparing phosphate iron lithium provided by the invention to be described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
1, with the absolute ethyl alcohol be dispersion agent, with 1.02mol monometallic, 0.4mol Ferrox, 0.255mol red stone and 0.09mol ironic citrate through the high speed ball mill ball mill mixing;
2, mixed raw material is placed tubular oven, feed nitrogen, be warming up to 350 ℃ as shielding gas, constant temperature 10 hours, the cooling back is ground and is obtained reacting precursor;
3, step 2 gained reaction precursor body is put into reactor drum, place tube furnace, feed nitrogen as shielding gas, be warming up to 700 ℃, constant temperature 24 hours behind the furnace cooling, grinds, and sieves, and the gained powder is LiFePO 4 material.
Be illustrated in figure 1 as the XRD figure of the product of present embodiment preparation, can know that by figure iron lithium phosphate successfully prepares, and do not have Fe among the figure
2The diffraction peak of P explains that thus this method contained Fe
2The generation of P.
The size-grade distribution of the LiFePO 4 material of test present embodiment preparation, test result is: this iron lithium phosphate has the size-grade distribution in three intervals, is respectively low footpath peak 0.2～0.1um, middle footpath peak 0.1～2um, high footpath peak 2～10um.
Embodiment 2
1, with the absolute ethyl alcohol be dispersion agent, 1.02mol monometallic, 0.4mol Ferrox, 0.24mol red stone and 0.12mol ironic citrate is even through the high speed ball mill ball mill mixing;
2, mixed raw material is placed tube furnace, feed argon gas as shielding gas, be warming up to 250 ℃, constant temperature 10 hours obtains the reaction precursor body after cooling, the grinding;
3, the reaction precursor body that step 2 is made is put into reactor drum, places tube furnace, feeds nitrogen as shielding gas, is warming up to 800 ℃, calcining at constant temperature 32 hours, and furnace cooling, the back gained powder that grinds, sieves are LiFePO 4 material.
The size-grade distribution of the LiFePO 4 material of test present embodiment preparation, test result is: this iron lithium phosphate has the size-grade distribution in three intervals, is respectively low footpath peak 0.2～1um, middle footpath peak 1～3um, high footpath peak 3～10um.
Embodiment 3
1, with the absolute ethyl alcohol be dispersion agent, 1mol monometallic, 0.2mol Ferrox, 0.36mol red stone and 0.08mol ironic citrate is even through the high speed ball mill ball mill mixing;
2, mixed raw material is placed tubular oven, feed nitrogen, be warming up to 400 ℃ as shielding gas, constant temperature 5 hours, the cooling back is ground and is obtained reacting precursor;
3, step 2 gained reaction precursor body is put into reactor drum, place tube furnace, feed nitrogen as shielding gas, be warming up to 500 ℃, constant temperature 40 hours behind the furnace cooling, grinds, and the gained powder that sieves is LiFePO 4 material.
The size-grade distribution of the LiFePO 4 material of test present embodiment preparation, test result is: this iron lithium phosphate has the size-grade distribution in three intervals, is respectively low footpath peak 0.2～2um, middle footpath peak 2～4um, high footpath peak 4～10um.
Embodiment 4
1, with the absolute ethyl alcohol be dispersion agent, 1mol monometallic, 0.6mol Iron diacetate, 0.16mol red stone and 0.08mol ironic citrate is even through the high speed ball mill ball mill mixing;
2, mixed raw material is placed tubular oven, feed argon gas, be warming up to 300 ℃ as shielding gas, constant temperature 20 hours, the cooling back is ground and is obtained reacting precursor;
3, step 2 gained reaction precursor body is put into reactor drum, place tube furnace, feed nitrogen as shielding gas, be warming up to 650 ℃, constant temperature 10 hours behind the furnace cooling, grinds, and the gained powder that sieves is LiFePO 4 material.
The size-grade distribution of the LiFePO 4 material of test present embodiment preparation, test result is: this iron lithium phosphate has the size-grade distribution in three intervals, is respectively low footpath peak 0.2～3um, middle footpath peak 3～5um, high footpath peak 5～10um.
Embodiment 5
1, with the absolute ethyl alcohol be dispersion agent, 1mol monometallic, 0.58mol Ferrox, 0.16mol iron nitrate and 0.08mol ironic citrate is even through the high speed ball mill ball mill mixing;
2, mixed raw material is placed tubular oven, feed nitrogen, be warming up to 300 ℃ as shielding gas, constant temperature 20 hours, the cooling back is ground and is obtained reacting precursor;
3, step 2 gained reaction precursor body is put into reactor drum, place tube furnace, feed nitrogen as shielding gas, be warming up to 600 ℃, constant temperature 12 hours behind the furnace cooling, grinds, and the gained powder that sieves is iron phosphate powder.
The size-grade distribution of the LiFePO 4 material of test present embodiment preparation, test result is: this iron lithium phosphate has the size-grade distribution in three intervals, is respectively low footpath peak 0.2～4um, middle footpath peak 4～6um, high footpath peak 6～10um.
Embodiment 6
1, with the absolute ethyl alcohol be dispersion agent, 1mol monometallic, 0.2mol Ferrox, 0.2mol Iron diacetate, 0.14mol iron nitrate, 0.1mol red stone and 0.26mol ironic citrate with ethanol are dispersion agent, even through the high speed ball mill ball mill mixing;
2, mixed raw material is placed tubular oven, feed nitrogen, be warming up to 300 ℃ as shielding gas, constant temperature 15 hours, the cooling back is ground and is obtained reacting precursor;
3, step 2 gained reaction precursor body is put into reactor drum, place tube furnace, feed nitrogen as shielding gas, be warming up to 650 ℃, constant temperature 14 hours behind the furnace cooling, grinds, and the gained powder that sieves is iron phosphate powder.
LiFePO 4 material with embodiment 1～6 preparation is a positive electrode material respectively, processes CR2016 type button Experimental cell according to following method, and numbering is followed successively by A, B, B, D, E, F:
1, with positive electrode material and electrically conductive graphite super P and sticker PVDF by 8: 1: 1 mixed, be dissolved in the N-Methyl pyrrolidone (NMP), the back oven dry that stirs, pulverize, be pressed in aluminium and process positive plate on the net.
2, the positive plate that step 1 is made descends dry 5h at 130 ℃ in vacuum drying oven; With dried positive plate, in being full of the glove box of high-purity argon gas, assemble, obtain CR2016 type button Experimental cell with negative pole, polypropylene diaphragm and the electrolytic solution of metal lithium sheet preparation.Wherein supporting electrolyte is LiPF in the electrolytic solution
6, solvent is a NSC 11801 (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, the concentration of electrolytic solution 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
Can know that by The above results adopt the LiFePO 4 material of provider's method preparation of the present invention to have higher tap density and volume and capacity ratio, Fe2P impurity is few.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (9)
1. method preparing phosphate iron lithium comprises:
A), monometallic and source of iron are mixed, obtain the mixture material, the mol ratio of lithium and iron is (1～1.02) in the said mixture: (0.98～1); Said source of iron comprises: ferrous iron source compound, trivalent inorganic iron source compound and the organic Fe source compound of trivalent;
B), under protection of inert gas, said mixture material is heated 5h～20h under 300 ℃～500 ℃ condition, the cooling, obtain the reaction precursor body after the grinding;
C), under protection of inert gas, said reaction precursor body is calcined 10h～40h under 600 ℃～800 ℃ condition, the cooling, obtain iron phosphate powder after the grinding.
2. preparation method according to claim 1 is characterized in that, said ferrous iron source compound is Ferrox and/or Iron diacetate.
3. preparation method according to claim 1 is characterized in that, said trivalent inorganic iron source compound is red stone and/or iron nitrate.
4. preparation method according to claim 1 is characterized in that, the organic Fe source compound of said trivalent is an ironic citrate.
5. preparation method according to claim 1 is characterized in that, the mol ratio of said ferrous iron source compound, trivalent inorganic iron source compound and the organic Fe source compound of trivalent is (0.2～0.6): (0.16～0.36): (0.08～0.26).
6. preparation method according to claim 1 is characterized in that, the mode of blended described in the step a is the high speed ball mill mixing.
7. an anode material for lithium-ion batteries is characterized in that, its iron phosphate powder for being processed by the described method of claim 1.
8. a lithium ion cell positive is characterized in that, comprises matrix and the coating material that places matrix surface, and said coating material comprises: the described anode material for lithium-ion batteries of claim 7, electro-conductive material and caking agent.
9. a lithium ion battery is characterized in that, comprising: the described lithium ion cell positive of claim 8, negative pole and be arranged on barrier film and the electrolytic solution between said positive pole and the negative pole.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102751491A (en) * | 2012-07-03 | 2012-10-24 | 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 |
| CN111392705A (en) * | 2020-02-25 | 2020-07-10 | 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 |
| CN116081589A (en) * | 2022-10-12 | 2023-05-09 | 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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| CN102751491A (en) * | 2012-07-03 | 2012-10-24 | 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 |
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| CN109411707A (en) * | 2018-10-30 | 2019-03-01 | 郭和俊 | A kind of preparation method of LiFePO4 battery core |
| CN111392705A (en) * | 2020-02-25 | 2020-07-10 | 东莞东阳光科研发有限公司 | Preparation method of high-compaction lithium iron phosphate |
| 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 |
| CN116081589A (en) * | 2022-10-12 | 2023-05-09 | 北京钠谛科技有限公司 | Lithium-rich lithium iron manganese phosphate material and preparation method 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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