CN103400969A - Preparation method of lithium iron phosphate/carbon composite powder serving as anode material of high-performance lithium battery - Google Patents
Preparation method of lithium iron phosphate/carbon composite powder serving as anode material of high-performance lithium battery Download PDFInfo
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Abstract
The invention relates to a preparation method of lithium iron phosphate/carbon composite powder serving as an anode material of a high-performance lithium battery. The preparation method comprises the following steps of: mixing a high-energy phosphate compound serving as a raw material with trivalent ferric salt, then mixing with a lithium source, carrying out carbon source reduction thermal treatment under a nitrogen protective atmosphere, and synthesizing to obtain the lithium iron phosphate/carbon composite powder containing high-energy quantum dots. The preparation method has the advantages that lots of free energy released by hydrolyzing phosphate groups in the structure of the high-energy phosphate compound ensures that iron ions are adsorbed and combined to high-energy phosphate bonds in the high-energy phosphate compound biomacromolecule chains to form high-energy iron phosphate aggregates, and the electrochemical performance of the lithium iron phosphate anode material can be obviously improved. The lithium iron phosphate/carbon composite powder can be used for preparing a high-capacity lithium-ion battery.
Description
Technical field
The present invention relates to a kind of preparation method who contains the lithium iron phosphate/carbon composite granule of high energy quantum dot, belong to technical field of function materials.
Background technology
LiFePO4 (LiFePO
4) because having Stability Analysis of Structures, fail safe and Heat stability is good, low price, non-environmental-pollution, the advantage such as high temperature circulation good reversibility and be subject to people and pay close attention to greatly, be considered to have the high-capacity lithium-ion power battery positive electrode of application potential.But it also has the inferior positions such as preparation is more difficult, chemical property is poor.
Prepare at present LiFePO
4Method mainly contain: high temperature solid-state method, hydro thermal method, sol-gel process, coprecipitation, carbothermic method etc.The people such as Choi adopt sol-gel processing to synthesize LiFePO
4(referring to: Choi D, Kumta P N, Surfactant based sol-gel approach to nanostructured LiFePO
4For high rate Li-ion batteries.Journal of the Power Sources, 2007,163 (2): 1064-1069), the method chemical uniformity is good, heat treatment temperature is low, particle diameter is little and narrowly distributing, be easy to control, but dry shrink large, suitability for industrialized production is difficult, synthesis cycle is long.Coprecipitation is synthesized LiFePO
4Component is even, synthesis temperature is low, particle is thin, but tap density is little, seriously polluted; Hydro thermal method is synthesized LiFePO
4Have the phase homogeneous, diameter of particle is little, but be only limited to the preparation of a small amount of powder, need high-temperature high-pressure apparatus, cost is high.The people such as Wang adopt carbothermic method to synthesize LiFePO
4(referring to: Wang L, Liang G C, Ou X Q, Zhi X K, Zhang J P, Cui J Y, Effect of synthesis temperature on the properties of LiFePO
4/ C composites prepared by carbothermal reduction, Journal of the Power Sources, 2009,189 (1): 423-428), the method has overcome the high shortcoming of solid phase method cost, can improve material conductivity, but the reaction time is long, the product lack of homogeneity, particle is thicker; The synthetic LiFePO of the high temperature solid-state method of employing is arranged for this reason
4Report, simple to operation comparatively speaking, synthesis cycle is long, product batch quality stability is poor, the high in cost of production shortcoming but still exist.In addition, CN1635648A discloses a kind of preparation method of high-density spherical ferric lithium phosphate as anode material of lithium-ion battery, at first the method reacts synthesizing spherical or class ball shape ferric phosphate precursor by wet-chemical, then with lithium source, carbon source, doping metals compound, evenly mix, reducing atmosphere heat treatment obtains spherical LiFePO
4CN101339995A provides a kind of preparation method of lithium iron phosphate positive electrode material for lithium ion power cell, and the method is by adding micro-nano-metal-oxide or slaine, and the synthetic LiFePO of employing water system Wet technique
4.
Up to now, prior art mainly concentrates on existing synthetic technology is improved and LiFePO
4The modification aspect, do not make LiFePO
4The synthetic technology of material, aspect of performance produce significant substantial variation, therefore, and synthetic LiFePO
4Because its performance is undesirable, be difficult to meet the needs for high-capacity lithium-ion power batteries such as electric automobile, electric adjustment, Aero-Space and energy-storage batteries, be badly in need of that new breakthrough is arranged on synthetic technology, to significantly improving LiFePO
4Chemical property, thereby meet the needs of new energy field to the high-capacity lithium-ion power battery positive electrode.
Summary of the invention
For the deficiencies in the prior art, the anode material for lithium-ion batteries LiFePO that exists in order to solve prior art
4The problems such as conductivity and charging capacity are low, the invention provides a kind of preparation method who contains the lithium iron phosphate/carbon composite granule of high energy quantum dot.Prepare a kind of lithium iron phosphate/carbon composite granule that high performance anode material of lithium battery contains the high energy quantum dot that has.
The term explanation:
The high energy quantum dot: the high energy quantum dot described in the present invention refers in lithium iron phosphate/carbon composite granule particle that having particle diameter is that 1～6nm, its structure are in metastable high-energy nano particle-LiFePO4 particle.
High energy phosphate compound: referring to the phosphate cpd that stores higher-energy, is generally in when hydrolysis, to discharge free energy to be called high energy phosphate compound more than 5.0 kilocalories (20.9 kilojoule).
Technical scheme of the present invention is as follows:
A kind of preparation method of lithium iron phosphate/carbon composite granule of high-performance lithium cell positive material, step is as follows:
(1) by PO
4 3-Concentration is that the high energy phosphate compound solution of 0.1～0.5mol/L is cultivated 20～40min under 30 ℃～70 ℃ conditions, and is standby after chilling, is designated as A solution.
(2) according to FePO
4Stoichiometric proportion, add Fe in A solution
3+Concentration is the ferric salt solution of 0.4～0.8mol/L, and with watery hydrochloric acid, regulating pH value is 2.5～3.5, fully stirs and ageing 3～5h, makes it produce sediment, through separate wash after under 100～120 ℃ dry 2h, obtain the ferric phosphate powder.
(3) press LiFePO
4Stoichiometric proportion, add the lithium source in above-mentioned ferric phosphate powder, then add appropriate glucose or ascorbic acid, and fully ground and mixed is even, obtains the lithium iron phosphate/carbon composite precursor.
(4) by gained lithium iron phosphate/carbon composite precursor under nitrogen protection through 300～400 ℃ of heat treatment 1～2h, and then be warming up to 500～800 ℃ of heat treatment 2～4h, obtain the lithium iron phosphate/carbon composite granule.
Gained lithium iron phosphate/carbon composite granule, granular size 50～220 nanometers, be meso-hole structure, and mesoporous aperture is 10～40nm, in particle, contains metastable energy-rich phosphate iron lithium particle, and size is 1～6nm.
According to the present invention, preferred, the high energy phosphate compound in step (1) is trinosin (ATP), PEP or amine formyl phosphoric acid.
According to the present invention, preferred, the chilling described in step (1) is to adopt liquid nitrogen chilling 6～20min.
According to the present invention, preferred, the watery hydrochloric acid mass concentration described in step (2) is 15～20wt%.
According to the present invention, preferred, the trivalent iron salt in step (2) is iron chloride or ferric nitrate.
According to the present invention, preferred, described in step (3), the lithium source is lithium carbonate.
According to the present invention, preferred, step is pressed Fe in (3)
3+: the C mol ratio is (24～25): (1～1.5) adds glucose or ascorbic acid; Further preferred Fe
3+: the C mol ratio is 24:1.
The present invention is usingd the technical scheme of embodiment 1 as scheme most preferably.
adopt the inventive method, key technology is that biotechnology is combined with chemical synthesising technology, utilize the characteristics of macromolecular chain and contained three energy-rich phosphate bonds of high energy phosphate compound itself, source of iron is mixed with high energy phosphate compound solution, the a large amount of free energys that utilize the phosphate group hydrolysis in the high energy phosphate compound structure to discharge, iron ion absorption is attached on the energy-rich phosphate bond in high energy phosphate compound large biological molecule chain, form energy-rich phosphate iron granule, and then with lithium source solid phase mixing, under nitrogen protection atmosphere, through the carbon source heat of reduction, process, in the lithium iron phosphate/carbon complex matrix, form and be in the special high energy quantum dot of metastable state and its structure and performance, the heat chemistry that realizes biomass energy transforms.High energy phosphate compound is at LiFePO
4Building-up process in, not only played the nanostructure template effect, also for the preparation LiFePO
4Phosphorus source and carbon source are provided, and can have formed the high energy quantum dot that structure is different from performance, be conducive to the Li+ transmission, thereby can improve LiFePO
4The chemical property of positive electrode.
The lithium iron phosphate/carbon composite granule that contains the high energy quantum dot that the inventive method is prepared, its particle is meso-hole structure, and mesoporous aperture is about 10～40nm; It is laminar that powder granule is, granular size 50～220 nanometers, and thickness is 1～5 nanometer; In lithium iron phosphate/carbon composite granule particle, contain energy-rich phosphate iron lithium granule (high energy quantum dot), its size is 1～6nm; Its structure different from the lithium iron phosphate/carbon matrix (seeing circle part in Fig. 1 b), lattice fringe is different and unintelligible, and the lattice distorted is described, is in metastable state (energy is high).The conductance of the lithium iron phosphate/carbon composite material that contains the high energy quantum dot prepared by the inventive method is 2.3～2.8 * 10
-3S/cm, 0.1C initial charge specific capacity is up to 197～208mAh/g, and its coulomb efficiency is 95%～100%; After circulation 100 times, the 0.1C specific discharge capacity still can reach 157～179mAh/g, and its high charge-discharge specific capacity has all surpassed LiFePO
4Specific capacity theoretical value (170mAh/g).
Compared with the prior art, advantage of the present invention is take high energy phosphate compound as stay in place form, phosphorus source and carbon source, iron ion is combined with energy-rich phosphate bond and forms energy-rich phosphate iron granule, the heat chemistry that realizes biomass energy transforms, in the lithium iron phosphate/carbon complex matrix, form the high energy quantum dot, effectively improved the chemical property of lithium iron phosphate positive material.With lithium iron phosphate/carbon composite granule prepared by the present invention, as positive electrode, can be used for preparing high-capacity lithium-ion power battery etc.
The accompanying drawing explanation
Fig. 1 is the HRTEM photo of embodiment 1 synthetic powder, and b is the high multiple enlarged photograph in the part of a.
Fig. 2 is the XRD spectra of embodiment 1 synthetic powder.
Fig. 3 is nitrogen adsorption desorption spectrogram (a) and the graph of pore diameter distribution (b) of embodiment 1 synthetic powder.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited to this.
Embodiment 1,
By PO
4 3-Concentration is that the trinosin solution of 0.2mol/L is incubated 30min under 40 ℃, then puts into rapidly after liquid nitrogen chilling 10min standbyly, is designated as A solution.According to FePO
4Stoichiometric proportion, to the ferric chloride solution that adds 0.6mol/L in A solution, with 15wt% watery hydrochloric acid, regulating its pH value is 3, fully stir also ageing 4 hours, make it produce sediment, after separating washing under 120 ℃ dry 2 hours, obtain the ferric phosphate powder of ecru.Then, press LiFePO
4Stoichiometric proportion, add lithium carbonate in the phosphoric acid iron powder, then press Fe
3+: the C mol ratio is that the 24:1 ratio is added ascorbic acid, and ground and mixed is even, obtains the lithium iron phosphate/carbon presoma; Under nitrogen atmosphere protection by it in 350 ℃ of heat treatment 1.5h, then be warmed up to 700 ℃ of insulation 3h, obtain black lithium iron phosphate/carbon composite granule, through its crystalline phase of X-ray diffraction analysis, be olivine-type LiFePO
4, as shown in Figure 2.The products therefrom powder granule is meso-hole structure, and as shown in Figure 3, mesoporous aperture is about 10～37nm; Lithium iron phosphate particles in structure is laminar, granular size 50～200 nanometers, and thickness is 1～4 nanometer; In lithium iron phosphate/carbon composite granule particle, contain the high energy quantum dot, its size is 1～3nm, as shown in circle part in Fig. 1 b; The conductance of this lithium iron phosphate/carbon composite material is 2.8 * 10
-3S/cm, 0.1C initial charge specific capacity is 197mAh/g, and first discharge specific capacity is 197mAh/g, and its coulomb efficiency is 100%; After circulation 100 times, the 0.1C specific discharge capacity reaches 179mAh/g.
Embodiment 2,
By PO
4 3-Concentration is that the trinosin solution of 0.1mol/L is incubated 40min under 30 ℃, then puts into rapidly after liquid nitrogen chilling 6min standbyly, is designated as A solution.According to FePO
4Stoichiometric proportion, to the ferric chloride solution that adds 0.4mol/L in A solution, with 20wt% watery hydrochloric acid, regulating its pH value is 2.5, fully stir also ageing 5 hours, make it produce sediment, after separating washing under 120 ℃ dry 2 hours, obtain the ferric phosphate powder of ecru.Then, press LiFePO
4Stoichiometric proportion, add lithium carbonate in the phosphoric acid iron powder, then press Fe
3+: the C mol ratio is that the 25:1.5 ratio is added ascorbic acid, and ground and mixed is even, obtains the lithium iron phosphate/carbon presoma; Under nitrogen atmosphere protection by it in 300 ℃ of heat treatment 2h, then be warmed up to 800 ℃ of insulation 2h, obtain black lithium iron phosphate/carbon composite granule.Analyze after tested, the mesoporous aperture of powder granule is about 16～34nm; Lithium iron phosphate particles in structure is laminar, granular size 70～180 nanometers, and thickness is 2～4 nanometers; In lithium iron phosphate/carbon composite granule particle, contain the high energy quantum dot, its size is 2～5nm.The conductance of this lithium iron phosphate/carbon composite material is 2.4 * 10
-3S/cm, 0.1C initial charge specific capacity is 202mAh/g, and first discharge specific capacity is 199mAh/g, and its coulomb efficiency is 98.5%; After circulation 100 times, the 0.1C specific discharge capacity reaches 162mAh/g.
Embodiment 3,
By PO
4 3-Concentration is that the trinosin solution of 0.5mol/L is incubated 20min under 70 ℃, then puts into rapidly to take out after liquid nitrogen chilling 20min standbyly, is designated as A solution.According to FePO
4Stoichiometric proportion, to the ferric chloride solution that adds 0.8mol/L in A solution, with 17wt% watery hydrochloric acid, regulating its pH value is 3.5, fully stir also ageing 3 hours, make it produce sediment, after separating washing under 100 ℃ dry 2 hours, obtain the ferric phosphate powder of ecru.Then, press LiFePO
4Stoichiometric proportion, add lithium carbonate in the phosphoric acid iron powder, then press Fe
3+: the C mol ratio is that the 23:1.2 ratio is added ascorbic acid, and ground and mixed is even, obtains the lithium iron phosphate/carbon presoma; Under nitrogen atmosphere protection by it in 400 ℃ of heat treatment 1h, then be warmed up to 600 ℃ of insulation 4h, obtain black lithium iron phosphate/carbon composite granule.Analyze after tested, the mesoporous aperture of powder granule is about 12～39nm; Lithium iron phosphate particles in structure is laminar, granular size 65～210 nanometers, and thickness is 3～5 nanometers; In lithium iron phosphate/carbon composite granule particle, contain the high energy quantum dot, its size is 3～6nm; The conductance of this lithium iron phosphate/carbon composite material is 2.3 * 10
-3S/cm, 0.1C initial charge specific capacity is 197mAh/g, and first discharge specific capacity is 193mAh/g, and its coulomb efficiency is 98%; After circulation 100 times, the 0.1C specific discharge capacity reaches 157mAh/g.
Embodiment 4,
As described in Example 1, difference is that high energy phosphate compound trinosin solution is changed to PEP solution, and other condition is with embodiment 1.Products therefrom lithium iron phosphate/carbon composite granule is analyzed after tested, and the mesoporous aperture of powder granule is about 11～36nm; Lithium iron phosphate particles in structure is laminar, granular size 85～220 nanometers, and thickness is 1～3 nanometer; In lithium iron phosphate/carbon composite granule particle, contain the high energy quantum dot, its size is 1～4nm; The conductance of this lithium iron phosphate/carbon composite material is 2.5 * 10
-3S/cm, 0.1C initial charge specific capacity is 208mAh/g, and first discharge specific capacity is 197mAh/g, and its coulomb efficiency is 94.9%; After circulation 100 times, the 0.1C specific discharge capacity reaches 159mAh/g.
As described in Example 1, difference is that high energy phosphate compound trinosin solution is changed to amine formyl phosphoric acid solution, and source of iron iron chloride is changed to ferric nitrate, and the reducing agent ascorbic acid is changed to glucose, and other condition is with embodiment 1.Products therefrom lithium iron phosphate/carbon composite granule is analyzed after tested, and the mesoporous aperture of powder granule is about 10～40nm; Lithium iron phosphate particles in structure is laminar, granular size 100～210 nanometers, and thickness is 2～5 nanometers; In lithium iron phosphate/carbon composite granule particle, contain the high energy quantum dot, its size is 2～6nm; The conductance of this lithium iron phosphate/carbon composite material is 2.3 * 10
-3S/cm, 0.1C initial charge specific capacity is 199mAh/g, and first discharge specific capacity is 190mAh/g, and its coulomb efficiency is 95.5%; After circulation 100 times, the 0.1C specific discharge capacity reaches 158mAh/g.
Claims (8)
1. the preparation method of a high-performance lithium battery anode material of lithium iron phosphate/carbon composite powder, step is as follows:
(1) by PO
4 3-Concentration is that the high energy phosphate compound solution of 0.1～0.5mol/L is cultivated 20～40min under 30 ℃～70 ℃ conditions, and is standby after chilling, is designated as A solution; .
(2) according to FePO
4Stoichiometric proportion, add Fe in A solution
3+Concentration is the ferric salt solution of 0.4～0.8mol/L, and with watery hydrochloric acid, regulating pH value is 2.5～3.5, fully stirs and ageing 3～5h, makes it produce sediment, through separate wash after under 100～120 ℃ dry 2h, obtain the ferric phosphate powder;
(3) press LiFePO
4Stoichiometric proportion, add the lithium source in above-mentioned ferric phosphate powder, then add appropriate glucose or ascorbic acid, and fully ground and mixed is even, obtains the lithium iron phosphate/carbon composite precursor;
(4) by gained lithium iron phosphate/carbon composite precursor under nitrogen protection through 300～400 ℃ of heat treatment 1～2h, and then be warming up to 500～800 ℃ of heat treatment 2～4h, obtain the lithium iron phosphate/carbon composite granule.
2. preparation method according to claim 1, is characterized in that the high energy phosphate compound in step (1) is trinosin (ATP), PEP or amine formyl phosphoric acid.
3. preparation method according to claim 1, is characterized in that using liquid nitrogen chilling 6～20min after the high energy phosphate compound solution heat treated in step (1).
4. preparation method according to claim 1, is characterized in that the trivalent iron salt in step (2) is iron chloride or ferric nitrate.
5. preparation method according to claim 1, is characterized in that the watery hydrochloric acid mass concentration described in step (2) is 15～20wt%.
6. preparation method according to claim 1, is characterized in that described in step (3), the lithium source is lithium carbonate.
7. preparation method according to claim 1, is characterized in that pressing Fe in step (3)
3+: the C mol ratio is (24～25): (1～1.5) adds glucose or ascorbic acid.
8. preparation method according to claim 1, is characterized in that pressing Fe in step (3)
3+: the C mol ratio is that 24:1 adds glucose or ascorbic acid.
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Cited By (6)
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| CN104393256A (en) * | 2014-09-30 | 2015-03-04 | 齐鲁工业大学 | Preparation method of lithium iron phosphate. lithium vanadium phosphate/carbon in-situ composite positive pole material |
| CN105720247A (en) * | 2016-02-03 | 2016-06-29 | 齐鲁工业大学 | Preparation method of composite cathode material for lithium-sodium mixed ion battery |
| CN108598418A (en) * | 2018-04-24 | 2018-09-28 | 齐鲁工业大学 | A kind of unformed NaVOPO of anode material of lithium-ion battery4/ C and the preparation method and application thereof |
| CN111056544A (en) * | 2019-12-16 | 2020-04-24 | 合肥国轩高科动力能源有限公司 | Sodium iron phosphate composite material and preparation method and application thereof |
| CN111525102A (en) * | 2019-12-04 | 2020-08-11 | 南通鼎鑫电池有限公司 | Preparation method of carbon quantum dot modified LiFePO4 positive electrode material |
| CN114275755A (en) * | 2021-12-14 | 2022-04-05 | 河源职业技术学院 | Method for preparing lithium iron phosphate by taking eggshell inner membrane as template |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104393256A (en) * | 2014-09-30 | 2015-03-04 | 齐鲁工业大学 | Preparation method of lithium iron phosphate. lithium vanadium phosphate/carbon in-situ composite positive pole material |
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| CN111056544A (en) * | 2019-12-16 | 2020-04-24 | 合肥国轩高科动力能源有限公司 | Sodium iron phosphate composite material and preparation method and application thereof |
| CN111056544B (en) * | 2019-12-16 | 2022-11-04 | 合肥国轩高科动力能源有限公司 | Sodium iron phosphate composite material and preparation method and application thereof |
| CN114275755A (en) * | 2021-12-14 | 2022-04-05 | 河源职业技术学院 | Method for preparing lithium iron phosphate by taking eggshell inner membrane as template |
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