CN108400310A - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents

A kind of anode material for lithium-ion batteries and preparation method thereof Download PDF

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CN108400310A
CN108400310A CN201810215748.1A CN201810215748A CN108400310A CN 108400310 A CN108400310 A CN 108400310A CN 201810215748 A CN201810215748 A CN 201810215748A CN 108400310 A CN108400310 A CN 108400310A
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lithium
preparation
anode material
ion batteries
graphene
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CN108400310B (en
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邓凌峰
彭辉艳
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HUNAN XINENG NEW MATERIAL Co.,Ltd.
Lianyuan Shenneng New Material Co.,Ltd.
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Hunan Allen New Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of anode material for lithium-ion batteries and preparation method thereof, the present invention provides the preparation methods with three-dimensional continuous stereo conductive network structure lithium iron phosphate positive electrode, i.e. with the lithium iron phosphate positive material of three-dimensional continuous stereo conductive network structure, substitution only relies on conductive agent to improve the limitation of electric conductivity at present, to improve the electron conduction and ionic conductivity of lithium iron phosphate positive material, to reach the specific discharge capacity and high-rate charge-discharge capability and cycle performance that improve lithium iron phosphate positive material, reduce its irreversible capacity, lithium iron phosphate positive material made from the method has high specific capacity, excellent cycle performance, the characteristics such as high rate performance and security performance, be especially suitable in the positive electrode of lithium-ion-power cell.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, more particularly to one kind to have three-dimensional continuous The preparation method of three-dimensional conductive network structure lithium iron phosphate positive electrode.
Background technology
Anode material for lithium-ion batteries LiFePO4And have a safety feature, cheap, higher specific capacity and charge and discharge Voltage platform is stable, the advantages that having extended cycle life.But due to LiFePO4Itself poor electronic conductivity and ionic conductivity make Its high rate capability is poor, and causes lower actual specific capacity (for 100mAh/g or so when actual specific capacity 1C, and theoretical specific volume Amount be 170mAh/g) and lower operating voltage (be 3.0V when actual discharge voltage 1C hereinafter, and theoretical discharge voltage is 3.4V), and during high current charge-discharge capacity can decline rapidly, to limit being widely used for it.Current is wide General research is to carry out surface cladding to it and the methods of bulk phase-doped improve its conductivity and ion diffusion rates.
The country is countless for patent of the graphene in terms of lithium ion battery, and the patent in terms of LiFePO4 is also very It is more, it is much better than organic carbon with graphene coated modified phosphate iron lithium electric conductivity；And on the basis of graphene to graphene into Row modification, patent (CN102569725A, CN107068990A, CN107180965A etc.) to graphene be fluorinated, The methods of porous, N doping cladding improves LiFePO4, improves the uniformity of graphene coated, improves the compatibility with electrolyte And structural stability；And patent CN105226276A, CN106129405A, CN104134801A are by nano-metal particle, gold Belong to the collaboration common coating-doping modified phosphate iron lithium of graphene such as oxide, nitride, the intervention of nano-particle further strengthens The electric conductivity and graphene dispersion of LiFePO4.The above method is substantially all to use water based on source of iron, phosphorus source, lithium source Hot method, ball-milling method, the method for dissolving prepare LiFePO4 and form three-dimensional conductive network knot in its surface coated graphite alkene composite material Structure enhances its electric conductivity, improves the electrochemistry such as specific capacity, high rate performance, the cyclical stability of LiFePO4 to a certain extent Performance.
The conversion ratio that the ferric ion from source of iron is all not involved in all invention at present considers, thus the present invention from This angle is set out, and obtains active catalytic nano-particle graphene using induction anchor titration first, then urged with new type high temperature solid phase It is combined to method, graphene/LiFePO of the three-dimensional continuous stereo conductive network structure of catalysis reaction synthesis in high-temperature atmosphere furnace4Just Pole material, material crystalline is preferable, and processing performance is stablized excellent with batch.
Explanation of nouns：
The graphene of functionalization：Finger introduces corresponding functional group or small point on the surface of graphene as needed Son contributes to graphene as the performance of reinforcement excellent performance, and principle is exactly using covalently with non-covalent method to stone The defect or group on black alkene surface are modified, and the certain new properties of graphene are assigned, improve graphene dissolubility, dispersibility with And keep its easier to process and molding important method.
Invention content
The present invention is precisely in order to overcome anode material for lithium-ion batteries LiFePO4Specific discharge capacity, high rate capability, follow Ring performance and the defects of irreversible capacity is higher and processing performance is poor, provides with three-dimensional continuous stereo conductive network structure The preparation method of lithium iron phosphate positive material is replaced with the lithium iron phosphate positive material of three-dimensional continuous stereo conductive network structure Only rely on conductive agent at present to improve the limitation of electric conductivity, to improve lithium iron phosphate positive material electron conduction and from Subconductivity rate, to reach the specific discharge capacity and high-rate charge-discharge capability and cyclicity that improve lithium iron phosphate positive material Can, its irreversible capacity is reduced, lithium iron phosphate positive material has high specific capacity, excellent cyclicity made from the method The characteristics such as energy, high rate performance and security performance, be especially suitable in the positive electrode of lithium-ion-power cell.
To achieve the above object, shown in technical scheme is as follows：
A kind of preparation method of anode material for lithium-ion batteries, includes the following steps：
Step 1: in the graphene to decentralized medium of dissolving functionalization, suspending liquid A is formed；
Step 2: the solution of active catalytic nano-particle is mixed with solution A, make the orientation anchoring of active catalytic nano-particle In the unsaturated sites and defect of graphene, active catalytic nano-particle is nano metal ion or nano metal ion complexation Object；Then reducing agent is added so that active catalytic nano-particle is reduced in the unsaturated sites of graphene and defective locations At metallic atom, solution B is formed；
Step 3: solution B is mixed with ferric phosphate, lithium source with one-dimensional nano line, is dried, it is sintered under protective gas atmosphere High temperature solid-state catalysis reaction is carried out, is then cooled to room temperature, that is, obtains final product graphene/iron lithium phosphate compound anode material Material.
It is further to improve, in the step 1, decentralized medium be methanol, ethyl alcohol, acetone, benzene, toluene, water, organic acid, One or more of organic ester.
Further to improve, in the step 1, graphene is added in decentralized medium, then 1~3h of ultrasonic disperse, shape At the suspending liquid A of stable dispersion.
Further to improve, in the step 2, active catalytic nano-particle is Pt (NH3)2+, Rh (NH3)5Cl2+)、 AuCl4 1-、[PbCl4]2-、[Co(NH3)4]2+、[Ni(NH3)4]2+[Ag(NH3)2]+、Rb6(CO)6、Ru3(CO)l2、PbSe、 CoC2O4One or more of.
It is further to improve, in the step 2, diameter grain ranging from 5~10nm of active catalytic nano-particle.
Further to improve, in the step 2, reducing agent is one in sodium borohydride, hydrazine hydrate, glucose, citric acid Kind is several.
It is further to improve, in the step 2, lithium source Li2CO3And/or LiOH.
It is further to improve, in the step 2, one-dimensional nano line carbon nanotube and/or cellulose.
Further to improve, in the step 3, the reaction temperature of high temperature solid-state catalysis reaction is 650-850 DEG C of temperature, Reaction time 6-8h.
Anode material for lithium-ion batteries made from a kind of preparation method of above-mentioned anode material for lithium-ion batteries.
The preparation technology figure of graphene/LiFePO4 of three-dimensional continuous stereo conductive network structure such as attached drawing 1, it is specific real Apply that steps are as follows：The preparation of active catalytic nano-particle graphene.High load is prepared using a kind of novel induction anchor titration to live Property catalytic nanoparticles graphene.Graphene is subjected to structure function processing, is formed using galvanoplastic induction graphene surface The unsaturated sites and defect of a large amount of ordered arrangement, such active catalytic nanoparticle, which can orient, is anchored on graphene-structured On, and graphene carrier height is made to disperse, then by reducing agent, make active catalytic nano-particle in graphene unsaturated sites and It is reduced on the position of defect, obtains the active catalytic nano-particle graphene with dual high catalytic action.
In above-mentioned preparation method, it is preferred that the active catalytic nano-particle is nano metal ion or complex compound Co2+、Ni2+、Pt(NH3)2+, Rh (NH3)5Cl2+)、AuCl4 1-、[PbCl4]2-、[Co(NH3)4]2+、[Ni(NH3)4]2+[Ag (NH3)2]+、Rb6(CO)6、Ru3(CO)l2、PbSe、CoC2O4One or more of.The size controlling of active catalytic nano-particle Between 5~10nm.
The present invention has outstanding characteristic below and strategic structural point：
1. the present invention develops a kind of novel induction anchor titration and prepares graphene-supported active catalytic nano-particle, will live Property catalytic nanoparticles high-sequential dispersion and strong anchoring in graphene-structured, enable active catalytic nano-particle efficiently and directionally Performance catalytic action.
2. ferric ion is to ferrous ion in graphene-supported active catalytic nano-particle energy efficient catalytic source of iron Conversion obtains the LiFePO4 of high-purity, and improves synthesis efficiency.Active catalytic nano-particle graphene-supported simultaneously Become chain carrier site in high-temperature reaction process, can effectively adsorb neighbouring source of iron and lithium source synthesizes phosphoric acid here Iron lithium, and be entrained in LiFePO4 body construction.The solid of the aobvious huge electric conductivity and lithium ion for improving LiFePO 4 material Memory space improves the specific capacity and stable circulation performance of material.
3. because the two-sided all supported actives catalytic nanoparticles of graphene with one-dimensional nano line, phosphorus source Fe source compound, lithium In the mixing in source and reaction process can precisely control form three-dimensional continuous stereo conductive network structure so that lithium iron phosphate particles and Surface is connected into unified entirety by graphene and one-dimensional nano line, ensure that the homogeneity of product batches.
4. three-dimensional continuous stereo conductive network structure graphite alkene/lithium iron phosphate positive material that the present invention obtains, electrochemistry The results show that specific discharge capacity is up to about 175mAh/g under 0.1C multiplying powers, specific discharge capacity still has under 20C multiplying powers 130mAh/g or so, big high rate performance is superior, and compared with the lithium iron phosphate positive material on existing market, chemical property has Show huge raising.
Description of the drawings
The preparation technology figure of graphene/LiFePO4 of Fig. 1 three-dimensional continuous stereo conductive network structures；
Fig. 2 a are the electromicroscopic photograph of the lithium iron phosphate positive material coated by embodiment 1；
The stereoscan photograph for the lithium iron phosphate positive material that Fig. 2 b are coated by embodiment 1；
Fig. 3 is bent by the charge and discharge of 0.1C, 0.5C, 1C, 5C, 10C, 20C of lithium iron phosphate positive material prepared by embodiment 1 Line.
Specific implementation mode
Embodiment 1
A kind of graphene/LiFePO of the three-dimensional continuous stereo conductive network structure of the present invention4Composite positive pole, graphite Alkene supported active catalytic nanoparticles and one-dimensional nano line modified synergic simultaneously pass through high temperature solid-state catalysis method synthesizing graphite alkene/phosphoric acid Iron lithium ion battery positive electrode.
As shown in Figure 1, this example is as follows：
(1) graphene by 2.5g Jing Guo functionalization is added in the ethanol solution of 500ml, and 1~3h of ultrasonic disperse makes It forms the suspending liquid A of stable dispersion；
(2) 11.51g active catalytic nano nickel ionic compounds are dissolved in 250ml deionized waters, mix, makes with solution A Active catalytic nanoparticle orientation is anchored in the unsaturated sites and defect of graphene, will be active by reducing agent sodium borohydride Catalytic nanometer ion is reduced into metallic atom in the unsaturated sites of graphene and defective locations, forms solution B；
(3) B solution is uniformly mixed with ferric phosphate 478.61g, lithium carbonate 126.81g with one-dimensional nano line 5g, is being reacted Constant speed stirring and drying in device is subsequently placed in high temperature sintering furnace under protective gas atmosphere by high temperature solid-state catalysis reaction (temperature 650-850 DEG C of degree, reaction time 6-8h), after being cooled to room temperature, that is, obtain final product graphene/iron lithium phosphate compound anode Material.Its Electronic Speculum and scanning electron microscopic picture are as shown in Figure 2 a and 2 b.
Wherein B solution is with the mixing of ferric phosphate, lithium carbonate and one-dimensional nano line, furnace drying method in step (3)：B is molten Liquid with phosphorus source Fe source compound, lithium source, one-dimensional nano line by ultrasonic disperse, mix, mixture is transferred in reactor, point It dissipating and mixing temperature is 100 DEG C~200 DEG C, dispersion is 2~8h with incorporation time, disperses and mixes completely, and becomes powdered, Be cooled to room temperature, to obtain ferric lithium phosphate precursor powder, then be sintered.
In the present embodiment, the dosage of ferric phosphate, lithium carbonate and one-dimensional nano line is optimum amount, arbitrarily adjusts its dosage, Also graphene/iron phosphate compound anode material of lithium can be made, only purity and specific discharge capacity are smaller.
Through electro-chemical test, graphene/electric discharge of the LiFePO4 materials under 0.1C, 0.5C, 1C, 5C, 10C, 20C multiplying power Specific capacity is respectively 168mAh/g, 165mAh/g, 160mAh/g, 145mAh/g, 140mAh/g, 130mAh/g, electric discharge intermediate value electricity Pressure respectively 3.38V, 3.36V, 3.31V, 3.22V, 3.08V, 2.98V, as shown in Fig. 3.Table 1 is product and text in this example Present it is preferable with preferably compare currently on the market, gram volume is all improved, and especially in big multiplying power, gram volume carries It is high relatively aobvious huge.
Table 1 show this patent data compared with the quality of product in market and document：
Embodiment 2
A kind of graphene/LiFePO of the three-dimensional continuous stereo conductive network structure of the present invention4Composite positive pole, activity Catalytic nanoparticles graphene and one-dimensional nano line modified synergic simultaneously pass through high temperature solid-state catalysis method synthesizing graphite alkene/LiFePO4 Positive electrode.
This example is as follows：
(1) graphene by 2.5g Jing Guo functionalization is added in the ethanol solution of 500ml, and 1~3h of ultrasonic disperse makes It forms stable suspending liquid A；
(2) 16.56g active catalytic nanometer cobalt ionic compounds are dissolved in 250ml deionized waters, mix, makes with solution A Active catalytic nanoparticle orientation is anchored in the unsaturated sites and defect of graphene, forms solution B；
(3) B solution is uniformly mixed with ferric phosphate 478.61g, lithium carbonate 126.81g with one-dimensional nano line 5g, will be mixed Object constant speed stirring and drying in the reactor, it is then solid by high temperature under protective gas atmosphere in being subsequently placed at high temperature sintering furnace Phase catalytic reaction (650-850 DEG C of temperature, reaction time 6-8h) after being cooled to room temperature, that is, obtains final product graphene/phosphoric acid Iron lithium composite positive pole.
The description of the above examples is only intended to facilitate the understand of the core idea of the present invention；Meanwhile for the general of this field Technical staff, according to the thought of the present invention, there will be changes in the specific implementation manner and application range, in conclusion The content of the present specification should not be construed as limiting the invention.

Claims (10)

1. a kind of preparation method of anode material for lithium-ion batteries, which is characterized in that include the following steps：
Step 1: in the graphene to decentralized medium of dissolving functionalization, suspending liquid A is formed；
Step 2: the solution of active catalytic nano-particle is mixed with solution A, active catalytic nano-particle orientation is made to be anchored on stone In the unsaturated sites and defect of black alkene, active catalytic nano-particle is nano metal ion or nano metal ionic complex； Then reducing agent is added so that active catalytic nano-particle is reduced into gold in the unsaturated sites of graphene and defective locations Belong to atom, forms solution B；
Step 3: solution B is mixed with ferric phosphate, lithium source with one-dimensional nano line, is dried, it is sintered and carries out under protective gas atmosphere High temperature solid-state catalysis reaction, is then cooled to room temperature, that is, obtains final product graphene/iron phosphate compound anode material of lithium.
2. the preparation method of anode material for lithium-ion batteries as described in claim 1, which is characterized in that in the step 1, Decentralized medium is one or more of methanol, ethyl alcohol, acetone, benzene, toluene, water, organic acid, organic ester.
3. the preparation method of anode material for lithium-ion batteries as described in claim 1, which is characterized in that in the step 1, Graphene is added in decentralized medium, then 1~3h of ultrasonic disperse, forms the suspending liquid A of stable dispersion.
4. the preparation method of anode material for lithium-ion batteries as described in claim 1, which is characterized in that in the step 2, Active catalytic nano-particle is Pt (NH3)2+, Rh (NH3)5Cl2+)、AuCl4 1-、[PbCl4]2-、[Co(NH3)4]2+、[Ni(NH3) 4]2+[Ag(NH3)2]+、Rb6(CO)6、Ru3(CO)l2、PbSe、CoC2O4One or more of.
5. the preparation method of anode material for lithium-ion batteries as described in claim 1, which is characterized in that in the step 2, Diameter grain ranging from 5~10nm of active catalytic nano-particle.
6. the preparation method of anode material for lithium-ion batteries as described in claim 1, which is characterized in that in the step 2, Reducing agent is one or more of sodium borohydride, hydrazine hydrate, glucose, citric acid.
7. the preparation method of anode material for lithium-ion batteries as described in claim 1, which is characterized in that in the step 2, Lithium source is Li2CO3And/or LiOH.
8. the preparation method of anode material for lithium-ion batteries as described in claim 1, which is characterized in that in the step 2, One-dimensional nano line is carbon nanotube and/or cellulose.
9. the preparation method of anode material for lithium-ion batteries as described in claim 1, which is characterized in that in the step 3, The reaction temperature of high temperature solid-state catalysis reaction is 650-850 DEG C of temperature, reaction time 6-8h.
10. lithium ion battery made from a kind of preparation method of any anode material for lithium-ion batteries of claim 1-9 is just Pole material.
CN201810215748.1A 2018-03-15 2018-03-15 Lithium ion battery anode material and preparation method thereof Active CN108400310B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109216673A (en) * 2018-08-19 2019-01-15 杭州电子科技大学 LiFePO4/multi-layer graphene composite material and preparation method and the lithium ion battery for applying it
CN115180609A (en) * 2022-08-11 2022-10-14 国环电池科技(苏州)有限公司 Lithium iron phosphate preparation process suitable for industrialization

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CN102185139A (en) * 2011-03-31 2011-09-14 中国科学院过程工程研究所 Preparation method of nanometer metallic oxide/graphene doped lithium iron phosphate electrode material
CN103066281A (en) * 2013-01-09 2013-04-24 上海交通大学 Synergistically modified lithium-iron-phosphate positive active material enveloped with graphene three-dimensional network and doped with metal ions and preparation method of lithium-iron-phosphate positive active material
CN103311541A (en) * 2012-03-08 2013-09-18 中国科学院金属研究所 Composite cathode material for lithium ion batteries and preparation method thereof
CN105226276A (en) * 2015-07-20 2016-01-06 合肥国轩高科动力能源有限公司 The preparation method of a kind of metal nanoparticle/Graphene composite lithium iron phosphate material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102185139A (en) * 2011-03-31 2011-09-14 中国科学院过程工程研究所 Preparation method of nanometer metallic oxide/graphene doped lithium iron phosphate electrode material
CN103311541A (en) * 2012-03-08 2013-09-18 中国科学院金属研究所 Composite cathode material for lithium ion batteries and preparation method thereof
CN103066281A (en) * 2013-01-09 2013-04-24 上海交通大学 Synergistically modified lithium-iron-phosphate positive active material enveloped with graphene three-dimensional network and doped with metal ions and preparation method of lithium-iron-phosphate positive active material
CN105226276A (en) * 2015-07-20 2016-01-06 合肥国轩高科动力能源有限公司 The preparation method of a kind of metal nanoparticle/Graphene composite lithium iron phosphate material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109216673A (en) * 2018-08-19 2019-01-15 杭州电子科技大学 LiFePO4/multi-layer graphene composite material and preparation method and the lithium ion battery for applying it
CN115180609A (en) * 2022-08-11 2022-10-14 国环电池科技(苏州)有限公司 Lithium iron phosphate preparation process suitable for industrialization
CN115180609B (en) * 2022-08-11 2023-12-15 华辰环保能源(广州)有限责任公司 Lithium iron phosphate preparation process suitable for industrialization

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