CN105552370A - Spherical cathode material for lithium-ion secondary battery and preparation method of spherical cathode material - Google Patents

Spherical cathode material for lithium-ion secondary battery and preparation method of spherical cathode material Download PDF

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CN105552370A
CN105552370A CN201610098941.2A CN201610098941A CN105552370A CN 105552370 A CN105552370 A CN 105552370A CN 201610098941 A CN201610098941 A CN 201610098941A CN 105552370 A CN105552370 A CN 105552370A
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lithium
ion secondary
secondary battery
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spherical
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CN105552370B (en
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唐月锋
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Suzhou Sun Source Nano Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1397Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to a spherical cathode material for a lithium-ion secondary battery and a preparation method of the spherical cathode material. The chemical composition of the spherical cathode material for the lithium-ion secondary battery is LiFe<x>Mn<1-x>PO<4>, x=0-1; the spherical structure is one of a solid sphere, a hollow sphere or a porous sphere; and the diameter is 5nm to 50 microns. The cathode material with a controllable spherical structure for the lithium-ion secondary battery is prepared by carrying out atomizing freeze-drying or atomizing heat-drying on a solution prepared from a lithium compound, an iron compound, a manganese compound, a phosphorus compound, a complexing agent and a carbon source and then carrying out high-temperature pyrolysis reaction. The preparation method provided by the invention can greatly shorten the sintering time of the cathode material for the lithium-ion secondary battery and avoids rapid growth of cathode material crystal for the lithium-ion secondary battery, so that the rapid charge-discharge performance of the cathode material for the lithium-ion secondary battery is improved. The cathode material for the lithium-ion secondary battery with the spherical structure is beneficial to subsequent preparation of a lithium-ion secondary all-battery, is also beneficial to full contact of the cathode material for the lithium-ion secondary battery and an electrolyte, shortens a diffusion path of lithium ions, and can improve the electrochemical properties of the cathode material for the lithium-ion secondary battery.

Description

Spherical lithium ion secondary battery positive electrode and preparation method thereof
Technical field
The present invention relates to spherical (medicine ball, hollow ball, porous ball) lithium ion secondary battery anode material [LiFe xmn 1-xpO 4, (x=1)] and be the lithium rechargeable battery manufacturing technology field of positive electrode, particularly a kind of spherical lithium ion secondary battery positive electrode [LiFe with special appearance xmn 1-xpO 4, (x=1)] and preparation method thereof.
Background technology
LiFe xmn 1-xpO 4it is one of first-selected positive electrode of power lithium-ion rechargeable battery, vigorously promoted the use by various countries in recent years, there is lot of advantages, as: there is very high discharge voltage, fast charging and discharging performance, high security, have extended cycle life, pollution-free, high-energy-density, memory-less effect.But affect LiFe xmn 1-xpO 4move towards the poorly conductive that practical shortcoming is it, be not suitable for high current charge-discharge.Current having improved one's methods two kinds: one is improve its electron conduction; Two is accelerate lithium ion diffusion rate.And by LiFe xmn 1-xpO 4positive electrode is prepared into special spherical structure, and the research as medicine ball, hollow ball and porous spherical is little.
Spherical LiFe xmn 1-xpO 4material is conducive to the preparation of the full battery of follow-up lithium ion secondary, also fully contacting of lithium ion secondary battery anode material and electrolyte is conducive to, shorten the evolving path of lithium ion, the time decreasing Lithium-ion embeding He deviate from, the chemical property of lithium ion secondary battery anode material can be improved.
LiFe xmn 1-xpO 4the preparation of positive electrode is generally that raw material obtains through high temperature sintering.Existing preparation LiFe xmn 1-xpO 4the method of positive electrode has a lot, and as solid-phase ball milling method, coprecipitation, Sol-Gel method etc., but these methods are all difficult to obtain special spherical LiFe xmn 1-xpO 4positive electrode.
Summary of the invention
The object of the invention is to provide spherical (medicine ball, hollow ball, porous ball) lithium ion secondary battery anode material [LiFe xmn 1-xpO 4, (x=1)] and preparation method, by preparing spherical (medicine ball, hollow ball, porous ball) lithium ion secondary battery anode material [LiFe xmn 1-xpO 4, (x=1)], improve the chemical property of lithium rechargeable battery in charge and discharge process.
The technical solution used in the present invention is as follows:
Spherical lithium ion secondary battery positive electrode, the chemical composition of this spherical lithium ion secondary battery positive electrode is: LiFe xmn 1-xpO 4, x=0 ~ 1, spherical structure is the one in medicine ball, hollow ball or porous ball, and diameter is 5nm ~ 50 μm.Preferably, hollow ball wall thickness is 1nm ~ 1 μm.
A preparation method for spherical lithium ion secondary battery positive electrode, it comprises the following steps:
1) by after lithium compound, iron compound, manganese compound, phosphorus compound, complexing agent and carbon source in proportion wiring solution-forming, through atomization, freeze drying or heat drying, collect and obtain powder;
2) by step 1) obtained powder carries out high-temperature quick solution, namely obtains pure phase spherical lithium ion secondary battery positive electrode.
Step 1) described in Li, the Fe in iron compound in lithium compound, the Mn in manganese compound, P, complexing agent and carbon source in phosphorus compound mol ratio be 1: x: 1-x: 1: (1.00 ~ 4.00): (0.01 ~ 1.00), (x=0 ~ 1).
Preferably, step 2) described in freeze drying temperature be-196 DEG C, heat drying is 350 DEG C, step 2) in pyrolysis temperature be 600 ~ 750 DEG C, pyrolysis time is 5 minutes.
Preferred further, described lithium compound is the one or more combination in lithium hydroxide, lithium acetate, lithium carbonate, lithium fluoride, lithium nitrate, lithium dihydrogen phosphate; Described iron compound is the one or more combination in di-iron trioxide, ferric nitrate, iron hydroxide, iron chloride, ferric sulfate, ferric phosphate, ferrous acetate, ferrous oxide, ferrous oxalate, ferrous sulfate; Described manganese compound is the one or more combination in manganese sesquioxide managnic oxide, manganese dioxide, manganous oxide, manganese nitrate, manganese phosphate, manganous hydroxide, manganese chloride, manganese sulfate, manganese acetate, manganese oxalate; Described phosphorus compound is the one or more combination in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, manganese phosphate, ferric phosphate, ammonium phosphate, lithium dihydrogen phosphate; Described complexing agent is the one or more combination in sulfuric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid; Described carbon source is the one or more combination in graphite microparticles, organic pyrolytic carbon, conductive carbon black, carbon nano-tube, carbon fiber, carbon cloth, carbon nanopowder, Graphene, fructose, sucrose, glucose, maltose, lactose, galactolipin, ribose, polysaccharide; Described solvent is the one or more combination in water, alkane, alcohol, ether, ketone, ester, aromatic hydrocarbon.
Described spherical (medicine ball, hollow ball, porous ball) lithium ion secondary battery anode material [LiFe xmn 1-xpO 4, (x=0 ~ 1)] apply as lithium ion secondary battery anode material.
Technological merit of the present invention is: the present invention by lithium compound, iron compound and or the solution that is made into of manganese compound, phosphorus compound, complexing agent and carbon source carry out atomization drying high temperature pyrolysis, obtain [the LiFe with spherical structure (medicine ball, hollow ball, porous ball) of morphology controllable xmn 1-xpO 4, (x=0 ~ 1)] and positive electrode.By high-temperature quick solution, suppress the fast growth of lithium ion secondary battery anode material crystal, thus improve the fast charging and discharging performance of lithium ion secondary battery anode material.And this structure can be conducive to [LiFe xmn 1-xpO 4, (x=0 ~ 1)] and positive electrode fully contacts with electrolyte, and shorten the diffusion path of lithium ion, can [LiFe be improved xmn 1-xpO 4, (x=0 ~ 1)] and the chemical property of positive electrode.
Accompanying drawing explanation
Fig. 1 is [LiFe xmn 1-xpO 4, (x=1)] XRD diffracting spectrum.
Fig. 2 is [LiFe xmn 1-xpO 4, (x=1)] and the SEM photo of medicine ball.
Fig. 3 is [LiFe xmn 1-xpO 4, (x=1)] and the SEM photo of porous ball.
Fig. 4 is [LiFe xmn 1-xpO 4, (x=1)] and the SEM photo of hollow ball.
Fig. 5 is [LiFe xmn 1-xpO 4, (x=1)] and discharge capacity curve under hollow ball different multiplying (0.1C, 0.5C, 1C, 5C, 10C, 20C).
Fig. 6 is [LiFe xmn 1-xpO 4, (x=1)] and discharge capacity under hollow ball different multiplying (0.1C, 0.5C, 1C, 5C, 10C, 20C) and cycle life performance curve.
Fig. 7 is [LiFe xmn 1-xpO 4, (x=0)] XRD diffracting spectrum.
Fig. 8 is [LiFe xmn 1-xpO 4, (x=0)] and the SEM photo of hollow ball.
Fig. 9 is [LiFe xmn 1-xpO 4, (x=0)] and discharge capacity curve under hollow ball different multiplying (0.05C, 0.1C, 0.2C, 0.5C, 1C, 2C, 5C).
Figure 10 is [LiFe xmn 1-xpO 4, (x=0)] and discharge capacity under hollow ball different multiplying (0.05C, 0.1C, 0.2C, 0.5C, 1C, 2C) and cycle life performance curve.
Figure 11 is [LiFe xmn 1-xpO 4, (x=0)] and cycle life performance curve under hollow ball 1C multiplying power.
Figure 12 is [LiFe xmn 1-xpO 4, (x=0.5)] and the SEM photo of medicine ball.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
The present invention by lithium compound, iron compound, manganese compound, phosphorus compound, complexing agent and carbon source with after certain proportion wiring solution-forming, through atomization drying (freeze drying or heat drying) high temperature pyrolysis, spherical (medicine ball, hollow ball, porous ball) lithium ion secondary battery anode material [LiFe directly can be obtained xmn 1-xpO 4, (x=0 ~ 1)].By high-temperature quick solution, suppress the fast growth of lithium ion secondary battery anode material crystal, thus improve the fast charging and discharging performance of lithium ion secondary battery anode material.Spherical (medicine ball, hollow ball, porous ball) lithium ion secondary battery anode material [LiFe can be prepared fast by the method xmn 1-xpO 4, (x=0 ~ 1)], and spherical (medicine ball, hollow ball, the porous ball) lithium ion secondary battery anode material [LiFe obtained xmn 1-xpO 4, (x=0 ~ 1)] diameter footpath and hollow ball wall thickness can be adjustable in very large scope, diameter is adjustable to 10 μm from 5nm, and wall thickness is adjustable to 1 μm from 1nm.
Embodiment 1
1. raw material takes: take 2.4g lithium hydroxide, 8.6g ferric phosphate, 3.2g glucose and 19.2g oxalic acid respectively, measure 500mL deionized water.
2. mix: the raw material taken above and deionized water are mixed, heating stirring and dissolving.
3. be atomized: above solution is poured in atomizer, atomization, form droplet, then droplet is incorporated into low-temperature space in freeze drier (-196 DEG C), obtains pressed powder.
4. dry: pressed powder is dry by freeze drier, by gained powder by fast pyrogenation in high temperature furnace, pyrolysis temperature is 750 DEG C, and pyrolysis time is 5 minutes, by gained [LiFe after pyrolysis xmn 1-xpO 4, (x=1)] and powder collection is for subsequent use.Its XRD diffracting spectrum is shown in Fig. 1, and SEM photo as shown in Figure 2.
Embodiment 2
1. raw material takes: take 3.9g lithium nitrate, 8.6g ferric phosphate, 3.2g glucose and 19.2g oxalic acid respectively, measure 1000mL deionized water.
2. mix: the raw material taken above and deionized water are mixed, heating stirring and dissolving.
3. be atomized: above solution is poured in atomizer, atomization, form droplet, then droplet is incorporated into low-temperature space in freeze drier (-196 DEG C), obtains pressed powder.
4. dry: pressed powder is dry by freeze drier, by gained powder by fast pyrogenation in high temperature furnace, pyrolysis temperature is 750 DEG C, and pyrolysis time is 5 minutes, by gained [LiFe after pyrolysis xmn 1-xpO 4, (x=1)] and powder collection is for subsequent use.Its SEM photo as shown in Figure 3.
Embodiment 3
1. raw material takes: take 4.2g lithium carbonate, 8.6g ferric phosphate, 3.2g glucose and 19.2g oxalic acid respectively, measure 1000ml deionized water.
2. mix: the raw material taken above and deionized water are mixed, heating stirring and dissolving.
3. be atomized: above solution is poured in atomizer, atomization, form droplet.
4. dry: then droplet is incorporated into (350 DEG C) in hot-blast stove dry, obtains pressed powder, gained pressed powder is passed through fast pyrogenation in high temperature furnace, pyrolysis temperature is 750 DEG C, and pyrolysis time is 5 minutes, by gained [LiFe after pyrolysis thereupon xmn 1-xpO 4, (x=1)] and powder collection is for subsequent use.As shown in Figure 4, as shown in Figure 5, the discharge capacity under different multiplying and cycle life performance are as shown in Figure 6 for the discharge capacity measured under different multiplying for its TEM photo.
Embodiment 4
1. raw material takes: take 5.9g lithium dihydrogen phosphate, 9.9g manganese acetate, 6.1g sucrose and 19.2g oxalic acid respectively, measure 500mL deionized water.
2. mix: the raw material taken above and deionized water are mixed, heating stirring and dissolving.
3. be atomized: above solution is poured in atomizer, atomization, form droplet, then droplet is incorporated into low-temperature space in freeze drier (-196 DEG C), obtains pressed powder.
4. dry: pressed powder is dry by freeze drier, by gained powder by fast pyrogenation in high temperature furnace, pyrolysis temperature is 600 DEG C, and pyrolysis time is 5 minutes, by gained [LiFe after pyrolysis xmn 1-xpO 4, (x=0)] and powder collection is for subsequent use.Its XRD diffracting spectrum is shown in Fig. 7, and as shown in Figure 8, as shown in Figure 9, as shown in Figure 10, under 1C multiplying power, cycle performance curve as shown in Figure 11 for the discharge capacity under different multiplying and cycle life performance for the discharge capacity measured under different multiplying for TEM photo.
Embodiment 5
1. raw material takes: take 2.4g lithium hydroxide, 4.3g ferric phosphate, 5.0g manganese acetate, 2.8g phosphoric acid, 6.1g sucrose and 19.2g oxalic acid respectively, measure 500mL deionized water.
2. mix: the raw material taken above and deionized water are mixed, heating stirring and dissolving.
3. be atomized: above solution is poured in atomizer, atomization, form droplet, then droplet is incorporated into low-temperature space in freeze drier (-196 DEG C), obtains pressed powder.
4. dry: pressed powder is dry by freeze drier, by gained powder by fast pyrogenation in high temperature furnace, pyrolysis temperature is 750 DEG C, and pyrolysis time is 5 minutes, by gained [LiFe after pyrolysis xmn 1-xpO 4, (x=0.5)] and powder collection is for subsequent use.Its SEM photo as shown in Figure 12.

Claims (9)

1. spherical lithium ion secondary battery positive electrode, is characterized in that: the chemical composition of this spherical lithium ion secondary battery positive electrode is: LiFe xmn 1-xpO 4, x=0 ~ 1, spherical structure is the one in medicine ball, hollow ball or porous ball, and diameter is 5nm ~ 50 μm.
2. spherical lithium ion secondary battery positive electrode according to claim 1, is characterized in that: hollow ball wall thickness is 1nm ~ 1 μm.
3. prepare a method for spherical lithium ion secondary battery positive electrode as claimed in claim 1 or 2, it is characterized in that: comprise the following steps:
1) by after lithium compound, iron compound, manganese compound, phosphorus compound, complexing agent, carbon source in proportion wiring solution-forming, through atomization, freeze drying or heat drying, collect and obtain powder;
2) by step 1) obtained powder carries out high-temperature quick solution, namely obtains pure phase spherical lithium ion secondary battery positive electrode.
4. the preparation method of spherical lithium ion secondary battery positive electrode according to claim 3, it is characterized in that: step 1) described in Li, the Fe in iron compound in lithium compound, the Mn in manganese compound, P, complexing agent and carbon source in phosphorus compound mol ratio be 1: x: (1-x): 1: (1.00 ~ 4.00): (0.01 ~ 1.00), x=0 ~ 1.
5. the preparation method of spherical lithium ion secondary battery positive electrode according to claim 3, is characterized in that: step 2) described in freeze drying temperature be-196 DEG C, heat drying is 350 DEG C.
6. the preparation method of spherical lithium ion secondary battery positive electrode according to claim 3, is characterized in that: step 2) in pyrolysis temperature be 600 ~ 750 DEG C, pyrolysis time is 5 minutes.
7. the preparation method of spherical lithium ion secondary battery positive electrode according to claim 3, is characterized in that: described lithium compound is selected from the one or more combination in lithium hydroxide, lithium acetate, lithium carbonate, lithium fluoride, lithium nitrate, lithium dihydrogen phosphate; Described iron compound is selected from the one or more combination in di-iron trioxide, ferric nitrate, iron hydroxide, iron chloride, ferric sulfate, ferric phosphate, ferrous acetate, ferrous oxide, ferrous oxalate, ferrous sulfate; Described manganese compound is selected from the one or more combination in manganese sesquioxide managnic oxide, manganese dioxide, manganous oxide, manganese nitrate, manganese phosphate, manganous hydroxide, manganese chloride, manganese sulfate, manganese acetate, manganese oxalate; Described phosphorus compound is selected from the one or more combination in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, manganese phosphate, ferric phosphate, ammonium phosphate, lithium dihydrogen phosphate; Described complexing agent is selected from the inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, the one or more combination in oxalic acid, acetic acid; Described carbon source is selected from the one or more combination in graphite microparticles, organic pyrolytic carbon, conductive carbon black, carbon nano-tube, carbon fiber, carbon cloth, carbon nanopowder, Graphene, fructose, sucrose, glucose, maltose, lactose, galactolipin, ribose, polysaccharide; Described solvent is selected from the one or more combination in water, alkane, alcohol, ether, ketone, ester, aromatic hydrocarbon.
8. the preparation method of spherical lithium ion secondary battery positive electrode according to claim 3, it is characterized in that: described lithium compound is the one in lithium hydroxide, lithium carbonate, lithium nitrate, lithium dihydrogen phosphate, described iron compound is ferric phosphate, described manganese compound is manganese acetate, and described phosphorus compound is the one in ferric phosphate, phosphoric acid, lithium dihydrogen phosphate.
9. an application for spherical lithium ion secondary battery positive electrode as claimed in claim 1, is characterized in that: as the positive electrode of lithium rechargeable battery.
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刘学文: ""溶胶凝胶法及超声雾化法制备LiFePO4/C正极材料的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 *

Cited By (9)

* Cited by examiner, † Cited by third party
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CN110323434A (en) * 2019-07-11 2019-10-11 江苏力泰锂能科技有限公司 Prepare iron manganese phosphate for lithium-carbon composite method and iron manganese phosphate for lithium-carbon composite
CN110323434B (en) * 2019-07-11 2022-07-22 江苏力泰锂能科技有限公司 Method for preparing lithium iron manganese phosphate-carbon composite material and lithium iron manganese phosphate-carbon composite material
CN111564320A (en) * 2020-05-20 2020-08-21 新昌县希亭科技有限公司 Nano MnO2Supercapacitor electrode material of modified carbon cloth and preparation method thereof
CN111564320B (en) * 2020-05-20 2023-01-31 新昌县希亭科技有限公司 Nano MnO 2 Supercapacitor electrode material of modified carbon cloth and preparation method thereof
CN114073919A (en) * 2020-08-19 2022-02-22 中国科学院理化技术研究所 Carbon-magnetic metal dispersion type hollow composite microsphere and preparation method and application thereof
CN114073919B (en) * 2020-08-19 2024-02-20 中国科学院理化技术研究所 Carbon-magnetic metal dispersion type hollow composite microsphere and preparation method and application thereof
CN113540410A (en) * 2021-07-12 2021-10-22 天津大学 Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method
CN114725374A (en) * 2022-03-31 2022-07-08 华为数字能源技术有限公司 Lithium iron phosphate material, preparation method thereof and battery
CN114725374B (en) * 2022-03-31 2024-05-03 华为数字能源技术有限公司 Lithium iron phosphate material, preparation method thereof and battery

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