CN102148371A - Graphene/phosphoric acid iron-lithium composite material with sandwich structure and preparation method thereof - Google Patents
Graphene/phosphoric acid iron-lithium composite material with sandwich structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a graphene/phosphoric acid iron-lithium composite material with a 'sandwich' structure and a preparation method thereof. The structure characteristics of the graphene/phosphoric acid iron-lithium composite material are that: blocky particles are formed by a grapheme laminated sheet which is completely coated by a phosphoric acid iron-lithium shell; and the insides of the particles present a similar 'sandwich' structure overlapped by a plurality of layers of phosphoric acid iron-lithium and graphene one by one. The preparation method thereof adopts a 'two-step' method. The characteristic steps are as follows: a graphene/phosphoric acid iron precursor with a 'sandwich' structure is compounded by a liquid phase method during the first step; then lithium is embedded in the second step; lithium iodide liquid phase low temperature reaction is adopted for embedding the lithium; then the graphene/phosphoric acid iron-lithium composite material is obtained through high temperature calcination under reducing (inertia) atmospheres; moreover, the graphene/phosphoric acid iron-lithium composite material can also be formed by the embedding of the lithium through high temperature solid phase reaction. The graphene/phosphoric acid iron-lithium composite material prepared by the method has high capacity and good charging-discharging circulating performances, and is suitable to be used as an anode material of a lithium ion battery.
Description
Technical field
The present invention relates to Graphene/composite ferric lithium phosphate material of a kind of sandwich structure and preparation method thereof, be suitable for preparing the positive electrode of lithium ion battery, belong to technical field of nano material.
Background technology
Lithium ion battery because have that voltage height, energy density are big, advantages such as good cycle, self discharge are little, memory-less effect, high performance-price ratio advantage with brilliance has occupied leading position in mobile electronic terminal apparatus field such as notebook computer, mobile phone, video cameras.Simultaneously, lithium ion battery also has broad prospects in the application of aspects such as electric automobile, uninterrupted power supply, large-scale communication power supply.
The raising of lithium ion battery performance mainly depends on the improvement of electrode material and the exploitation of new material.The transistion metal compound that contains lithium is the anode material for lithium-ion batteries the most widely of research at present, as LiCoO
2, LiNiO
2, LiMn
2O
4Deng.Because LiCoO
2Cost height, toxicity are big, and the resource of cobalt is few, have therefore limited its application on high capacity cell.LiNiO
2The shortcoming that preparation difficulty and poor heat stability are then arranged.Though LiMn
2O
4Compare LiCoO
2Cheapness and safety remain to be improved but reach the stable circulation performance because of its capacity is low, and is still undesirable on reality is used.
Goodenough reported first LiFePO from the upright university of Texas, USA in 1997
4Can be used as since the anode material for lithium-ion batteries, because it is cheap, the high theoretical capacity, environmentally friendly, and excellent cycle performance and thermal stability, caused that people pay close attention to widely.LiFePO
4Theoretical capacity reaches 170 mAh/g, to Li
+/ Li current potential is 3.5 V, and theoretical energy density reaches 580 Wh/Kg, is a kind of anode material for lithium-ion batteries that has application potential.But LiFePO
4The electronic conductivity (10 that material is low
-9~ 10
-10S/cm) and lithium ion diffusion coefficient (1.8x10
-14Cm
2/ S), cause its rate charge-discharge performance extreme difference, limited the application of this material.
People are by the conductivity of the whole bag of tricks raising LiFePO4, and corrective measure is mainly in the following aspects: mix high volence metal ion (as Mg in LiFePO 4 material
2+, Al
3+, Ni
2+, Mn
2+Deng), make the LiFePO4 intrinsic semiconductor change n type or p N-type semiconductor N into, conductivity of electrolyte materials can be improved 8 orders of magnitude; By adding conductive agent (carbon, metal dust etc.), as improve the electron conduction of material at particle surface coated with conductive carbon-coating; Particle diameter by control preparation material shortens the ion migration path, to reduce the ions diffusion time.
Graphene is as a kind of new carbon of two-dimentional hexagonal lattice structure, and it is the mono-layer graphite sheet of the bi-dimensional cellular shape grid that closely is arranged in by the sp2 carbon atom, has very high conductivity and bigger specific area.Graphene good electrical conductivity and stability have determined it to can be used as conducting base to prepare nano composite material, improve the conductivity of composite material.The two-dimensional nano layer structure of Graphene and bigger specific area make it aspect composite modification material again, the advantage that has nano particle or nano wire to be difficult to reach.In addition, Graphene prepares easily, cost is low, can be scattered in the aqueous solution in a large number, thereby makes the Graphene/composite ferric lithium phosphate material of a kind of excellent performance of preparation, becomes possibility to be applied to high performance lithium ion battery.
Summary of the invention
The purpose of this invention is to provide a kind of Graphene/composite ferric lithium phosphate material with unique " sandwich " structure, its typical structure is characterized as the Graphene synusia and is wrapped up the blocky-shaped particle (seeing accompanying drawing 2) that the back forms fully by the LiFePO4 shell: granule interior is the structure (seeing accompanying drawing 3) of the multiple-level stack of one deck LiFePO4/layer graphene similar " sandwich " that form.This material is to realize electrical conductivity by the satisfactory electrical conductivity as the Graphene lamella of composite construction inner skeleton, thereby improves the apparent conductivity of material.This material structure is different from general carbon-coated LiFePO 4 for lithium ion batteries material, and the carbon-coated LiFePO 4 for lithium ion batteries material only has the conductive carbon layer of skim at particle surface, and by the electrical conductivity between this thin carbon layer raising particle.
Its preparation method adopts " two-step method ", and its characterization step is: the first step is to adopt the Graphene/ferric phosphate presoma of synthetic " sandwich " structure of liquid phase method; Second step was an embedding lithium step, had two kinds of technologies can realize embedding lithium step: a kind of technology is to adopt lithium iodide liquid phase low temperature embedding lithium, and high-temperature calcination obtains Graphene/composite ferric lithium phosphate material under reduction (inertia) atmosphere then; Another kind of technology is to form Graphene/composite ferric lithium phosphate material by high temperature solid state reaction embedding lithium.Graphene/composite ferric lithium phosphate material capacity height, the charge-discharge performance of the inventive method preparation are good, are suitable for anode material for lithium-ion batteries.
The preparation technology that the inventive method is taked may further comprise the steps:
One, the Graphene/ferric phosphate presoma of synthetic " sandwich " structure of liquid phase method
A. take by weighing a certain amount of potassium peroxydisulfate and phosphorus pentoxide, be dissolved in the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide are 0.2 g/mL with respect to the ratio of the concentrated sulfuric acid; Behind 80 ℃ of insulation some hrs, an amount of natural graphite powder is added above-mentioned solution, the mass ratio of natural graphite powder and potassium peroxydisulfate is 1:1～2:1; Be cooled to room temperature, with deionized water dilution back standing over night; Filter the floating residual acid final vacuum drying of going;
B. above-mentioned product is dissolved in the concentrated sulfuric acid, adds potassium permanganate under condition of ice bath, the mass ratio of potassium permanganate and above-mentioned product is 2:1～4:1; 35 ℃ of constant temperature stir some hrs, leave standstill with the deionized water dilution again; Get an amount of 30wt%H
2O
2Add above-mentioned solution; Filtering the back is the HCl solution washing of 1:10 with volume ratio earlier, uses deionized water wash again;
C. above-mentioned solution is added the deionized water dilution, successively add a certain amount of water-soluble ferrous salt and water-soluble phosphorus-containing compound; Water-soluble ferrous salt and water-soluble phosphorus-containing compound are by contained separately Fe
2+With PO
4 3-Mol ratio be 1:1 batching, concentration is 0.01～0.1 mol/L of reaction system; Above-mentioned solution and the contained Fe of water-soluble ferrous salt
2+Ratio be 10～30 L/mol; The dissolving back adds an amount of 30wt%H
2O
2, stir some hrs under the room temperature, centrifugal and use the washed with de-ionized water several times, the gained paste places in the convection oven, 80 ℃ of dry some hrs;
Described water-soluble ferrous salt optimum is: any in ferrous sulfate, frerrous chloride or the iron ammonium sulfate;
Described water-soluble phosphorus-containing compound optimum is any in phosphoric acid, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate;
D. dried material is ground to form powdery; place tube furnace; under the condition of logical inert gas shielding, 200～800 ℃ of annealing natural cooling after 4～6 hours obtains removing the Graphene with typical case's " sandwich " structure/ferric phosphate composite material precursor of the crystallization water.
Two, the Graphene/LiFePO4 of synthetic " sandwich " structure of Graphene/ferric phosphate presoma embedding lithium
(1) low temperature liquid phase reaction embedding lithium processing step
E. get a certain amount of lithium iodide and be dissolved in an amount of acetonitrile, add the Graphene/ferric phosphate presoma after respective amount is annealed again; The mass ratio of lithium iodide and Graphene/ferric phosphate composite material is 2:1～4:1, and the concentration of LiI in acetonitrile is 0.2～1.0 mol/L; Stirred under the room temperature 10～24 hours, centrifugal and clean several times with acetonitrile, the gained precipitation places in the vacuum drying chamber 60～200 ℃ of dry some hrs;
F. above-mentioned dry gained material is placed tube furnace, at inert gas or reducing atmosphere (as Ar/H
2Volume ratio is 95:5) under, calcine natural cooling after 2 ~ 10 hours, obtain homodisperse Graphene/composite ferric lithium phosphate material for 500 ~ 800 ℃.
(2) step of high temperature solid state reaction embedding lithium technology
G. Graphene/ferric phosphate precursor and a certain proportion of lithium compound got after a certain amount of annealing fully mix, and the contained Li element and the mass ratio of Graphene/ferric phosphate composite material are 1:10～1:20 in the lithiumation thing.Then mixture is placed tube furnace, at inert atmosphere or reducing atmosphere (as Ar/H
2Volume ratio is 95:5) under, in 500～800 ℃ the calcining 2～10 hours after natural cooling, obtain homodisperse Graphene/composite ferric lithium phosphate material.
Lithium compound among the above-mentioned steps g is any in lithium carbonate, lithium hydroxide, lithia, the lithium acetate, by the stoichiometric proportion batching.
Prepared graphene/composite ferric lithium phosphate material of the present invention is characterised in that LiFePO
4Particle is a skeleton with the Graphene lamella, and evenly attached to graphene film laminar surface and complete coated graphite alkene lamella, the multiple-level stack of one deck LiFePO4/layer graphene forms the blocky-shaped particle with unique " sandwich " structure.Graphene film is in as the composite structure skeleton, also constitute the network of electron conduction, can greatly improve the electronic conductivity of material, reduced the material internal resistance, thereby improve the high rate capability of lithium ion battery, reach than the better modified effect of traditional means such as carbon coating.
The inventive method has following characteristics:
(1) the inventive method preparation technology is simple, does not add any catalyst and chemical initiator, and manufacturing cycle is short; Output is big, the productive rate height, but scale is used.
(2) FePO
4And LiFePO
4All can under liquid-phase condition, synthesize the effectively particle diameter of control material, and raising material purity; Technological temperature is low, reduces energy consumption.
(3) first synthesizing graphite alkene/ferric phosphate composite material obtains Graphene/composite ferric lithium phosphate material to its embedding lithium again, and unique " two-step method " preparation technology can control the pattern and the structure of composite material better, improves the electrical property of material.
Description of drawings
Fig. 1 is the XRD figure spectrum of Graphene/composite ferric lithium phosphate material.
Fig. 2 is the stereoscan photograph of the Graphene/LiFePO4 particle of typical case's " sandwich " structure.
Fig. 3 is the stereoscan photograph of the inner multiple-level stack structure of Graphene/composite ferric lithium phosphate material.
Fig. 4 is for being the charging and discharging curve of lithium ion battery under different multiplying of positive electrode with Graphene/composite ferric lithium phosphate material.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
Take by weighing potassium peroxydisulfate 2.5g, phosphorus pentoxide 2.5g is dissolved in the 12mL concentrated sulfuric acid, is heated to 80 ℃; The 3g natural graphite powder is added above-mentioned solution, and 80 ℃ are incubated 4 hours; Be cooled to room temperature, after the dilution of 500mL deionized water, standing over night; Filter in back 60 ℃ of vacuum drying chambers dry; Above-mentioned product is dissolved in the 120mL concentrated sulfuric acid, and 15g potassium permanganate is slowly added in the solution, and 35 ℃ were stirred 2 hours, slowly diluted with 250mL water again, left standstill 2 hours; With 20mLH
2O
2(30wt%) add above-mentioned solution; Filter and then be that the HCl solution 1L of 1:10 washs ultrasonic 15 minutes with volume ratio; Add the 5ml isopropyl alcohol, ultrasonic again 15 minutes, get Graphene solution.
Get the above-mentioned solution of 67mL, add deionized water and be diluted to 500mL, add 1.40 g FeSO
47H
2O stirs 10min under the room temperature, adds 0.58 g ammonium dihydrogen phosphate again, stirs 10min; Drip 0.31 g H
2O
2(30wt%); stirred 2 hours under the room temperature; centrifugal and with washed with de-ionized water three times; the gained paste is placed in the convection oven, and 80 ℃ of dryings ground to form powdery after 4 hours, placed tube furnace; under logical nitrogen protection condition; heating rate with 5 ℃/min is warming up to 400 ℃, and the natural cooling after 6 hours of annealing obtains removing the Graphene/ferric phosphate composite material of the crystallization water.
Get 2.01 g LiI and be dissolved in the 30mL acetonitrile, add the Graphene/ferric phosphate composite material after 0.75 g anneals again; Stirred under the room temperature 24 hours, centrifugal and clean 3 times with acetonitrile, the gained precipitation places in the vacuum drying chamber, and 60 ℃ of dryings were placed in the tube furnace in 2 hours, at reducing atmosphere (Ar/H
2Volume ratio is 95:5) under, be warming up to 600 ℃ with the heating rate of 5 ℃/min, calcine natural cooling after 2 hours, obtain homodisperse Graphene/composite ferric lithium phosphate material.
The XRD of product sees shown in Fig. 1, adopts this method as seen from the figure, has prepared the rhombic system olivine-type lithium iron phosphate positive material of pure phase, free from admixture peak in this product.Fig. 2 and Fig. 3 are the stereoscan photographs that makes composite material, and graphene film is wrapped within the shell of LiFePO 4 material formation fully, form the structure of similar " sandwich ", and granule interior also has multiple-level stack to form the structure of particle again.
With the lithium sheet is negative pole, and the product of gained is assembled into Experimental cell, and constant current charges and discharge its cycle performance (Fig. 4) of test.As shown in Figure 4, charge-discharge magnification is 0.1C, and when charging/discharging voltage was 2.5～4.2V, the discharge capacity after battery is stable reached 158mAh/g; High-rate charge-discharge capability excellence, 1C, 3C and 5C specific discharge capacity reach 146,134 and 123mAh/g.
Embodiment 2
Getting concentration is Graphene solution 56 mL of 3mg/mL, adds deionized water and is diluted to 500mL, adds 1.0 g FeCl
24H
2O stirs 10min under the room temperature, adds 0.61 g diammonium hydrogen phosphate again, stirs 10min; Drip 0.33g H
2O
2(30wt%); stirred 3 hours under the room temperature; centrifugal and with washed with de-ionized water three times; the gained paste is placed in the convection oven; 80 ℃ of dryings ground to form powdery after 5 hours, placed tube furnace, under logical nitrogen protection condition; 400 ℃ of annealing natural cooling after 4 hours obtains removing the Graphene/ferric phosphate composite material of the crystallization water.
Get 4.02 g LiI and be dissolved in the 60mL acetonitrile, add the Graphene/ferric phosphate composite material after 1.50 g anneal again; Stirred under the room temperature 12 hours, centrifugal and clean 3 times with acetonitrile, the gained precipitation places in the vacuum drying chamber, and 60 ℃ of dryings were placed in the tube furnace in 3 hours, at reducing atmosphere (Ar/H
2Volume ratio is 95:5) under, calcine natural cooling after 4 hours, obtain homodisperse Graphene/composite ferric lithium phosphate material for 600 ℃.The gained material is during with 1C and 5C multiplying power discharging, and specific capacity is respectively 141 and 120mAh/g.
Embodiment 3
Getting concentration is the Graphene solution 74mL of 3mg/mL, adds deionized water and is diluted to 500mL, adds 1.98 g Fe (NH
4)
2(SO
4)
26H
2O stirs 10min under the room temperature, adds 0.41 g phosphoric acid again, stirs 10min; Drip 0.27g H
2O
2(30wt%); stirred 4 hours under the room temperature; centrifugal and with washed with de-ionized water three times; the gained paste is placed in the convection oven; 80 ℃ of dryings ground to form powdery after 4 hours, placed tube furnace, under logical nitrogen protection condition; 400 ℃ of annealing natural cooling after 5 hours obtains removing the Graphene/ferric phosphate composite material of the crystallization water.
Get the Graphene/ferric phosphate composite material after 1.13 g anneal, the mol ratio of pressing Fe ion and Li ion 1:1 adds the lithium carbonate raw material, and fully ground and mixed is 1 hour, then mixture is placed tube furnace, at reducing atmosphere (Ar/H
2Volume ratio is 95:5) under, calcine natural cooling after 3 hours, obtain homodisperse Graphene/composite ferric lithium phosphate material for 600 ℃.The gained material is during with 1C and 5C multiplying power discharging, and specific capacity is respectively 148 and 127mAh/g.
Claims (7)
1. Graphene/the composite ferric lithium phosphate material of a sandwich structure, it is characterized in that: the Graphene synusia is wrapped up the blocky-shaped particle that the back forms fully by the LiFePO4 shell in this composite material, and granule interior is the sandwich structure of the multiple-level stack of one deck LiFePO4/layer graphene.
2. preparation method who is used for the Graphene/composite ferric lithium phosphate material of the described sandwich structure of claim 1 is characterized in that this method has following steps:
Graphene/ferric phosphate the presoma of the synthetic sandwich structure of liquid phase method
A. take by weighing a certain amount of potassium peroxydisulfate and phosphorus pentoxide, be dissolved in the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide are 0.2 g/mL with respect to the ratio of the concentrated sulfuric acid; Behind 80 ℃ of insulation some hrs, an amount of natural graphite powder is added above-mentioned solution, the mass ratio of natural graphite powder and potassium peroxydisulfate is 1:1～2:1; Be cooled to room temperature, with deionized water dilution back standing over night; Filter the floating residual acid final vacuum drying of going;
B. above-mentioned product is dissolved in the concentrated sulfuric acid, adds potassium permanganate under condition of ice bath, the mass ratio of potassium permanganate and above-mentioned product is 2:1～4:1; 35 ℃ of constant temperature stir some hrs, leave standstill with the deionized water dilution again; Get an amount of 30wt%H
2O
2Add above-mentioned solution; Filtering the back is the HCl solution washing of 1:10 with volume ratio earlier, uses deionized water wash again;
C. above-mentioned solution is added the deionized water dilution, successively add a certain amount of water-soluble ferrous salt and water-soluble phosphorus-containing compound; Water-soluble ferrous salt and water-soluble phosphorus-containing compound are by contained separately Fe
2+With PO
4 3-Mol ratio be 1:1 batching, concentration is 0.01～0.1 mol/L of reaction system; Above-mentioned solution and the contained Fe of water-soluble ferrous salt
2+Ratio be 10～30 L/mol; The dissolving back adds an amount of 30wt%H
2O
2, stir some hrs under the room temperature, centrifugal and use the washed with de-ionized water several times, the gained paste places in the convection oven, 80 ℃ of dry some hrs;
D. dried material is ground to form powdery, place tube furnace, under the condition of logical inert gas shielding, 200～800 ℃ of annealing natural cooling after 4～6 hours obtains removing the Graphene with sandwich structure/ferric phosphate composite material precursor of the crystallization water;
Graphene/the LiFePO4 of the synthetic sandwich structure of Graphene/ferric phosphate presoma embedding lithium
E. get a certain amount of lithium iodide and be dissolved in an amount of acetonitrile, add the Graphene/ferric phosphate presoma after respective amount is annealed again; The mass ratio of lithium iodide and Graphene/ferric phosphate composite material is 2:1～4:1, and the concentration of LiI in acetonitrile is 0.2～1.0 mol/L; Stirred under the room temperature 10～24 hours, centrifugal and clean several times with acetonitrile, the gained precipitation places in the vacuum drying chamber 60～200 ℃ of dry some hrs;
F. above-mentioned dry gained material is placed tube furnace, under inert gas or reducing atmosphere, calcine natural cooling after 2～10 hours, obtain homodisperse Graphene/composite ferric lithium phosphate material for 500～800 ℃.
3. method according to claim 2 is characterized in that the water-soluble ferrous salt described in the step c is a kind of in ferrous sulfate, frerrous chloride or the iron ammonium sulfate.
4. method according to claim 2 is characterized in that the water-soluble phosphorus-containing compound described in the step c is a kind of in phosphoric acid, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate.
5. method according to claim 2 is characterized in that the Graphene/LiFePO4 of the synthetic sandwich structure of described Graphene/ferric phosphate presoma embedding lithium adopts the step of high temperature solid state reaction embedding lithium technology as follows:
Graphene/ferric phosphate precursor and a certain proportion of lithium compound got after a certain amount of annealing fully mix, and the contained Li element and the mass ratio of Graphene/ferric phosphate composite material are 1:10～1:20 in the lithiumation thing; Then mixture is placed tube furnace, under inert atmosphere or reducing atmosphere, in 500～800 ℃ the calcining 2～10 hours after natural cooling, obtain homodisperse Graphene/composite ferric lithium phosphate material.
6. method according to claim 5 is characterized in that described lithium compound is any in lithium carbonate, lithium hydroxide, lithia, the lithium acetate.
7. according to claim 2 or 5 described methods, it is characterized in that described reducing atmosphere is Ar/H
2Volume ratio is 95:5.
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|---|---|---|---|---|
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| CN102544492A (en) * | 2011-03-07 | 2012-07-04 | 南京大学 | Lithium iron phosphate/graphene composite material with interlay sheet structure and preparation method and application thereof |
| CN102683697A (en) * | 2012-05-14 | 2012-09-19 | 中南大学 | Preparation method of graphene-based LiFePO4/C composite material |
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| CN109301177A (en) * | 2018-08-15 | 2019-02-01 | 湖南鸿跃电池材料有限公司 | A kind of stratiform composite ferric lithium phosphate material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800310A (en) * | 2010-04-02 | 2010-08-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing graphene-doped anode material for lithium-ion batteries |
| CN101944593A (en) * | 2010-09-15 | 2011-01-12 | 天津大学 | Positive pole material of lithium ion battery with nanometer structure and preparation method thereof |
-
2011
- 2011-03-03 CN CN2011100501482A patent/CN102148371A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800310A (en) * | 2010-04-02 | 2010-08-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing graphene-doped anode material for lithium-ion batteries |
| CN101944593A (en) * | 2010-09-15 | 2011-01-12 | 天津大学 | Positive pole material of lithium ion battery with nanometer structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| DENGYU PAN，ET AL.: "Li Storage Properties of Disordered Graphene Nanosheets", 《CHEMISTRY OF MATERIALS》, vol. 21, 6 July 2009 (2009-07-06), pages 3136 - 3142, XP055118138, DOI: doi:10.1021/cm900395k * |
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| CN102544492B (en) * | 2011-03-07 | 2015-04-08 | 南京大学 | Lithium iron phosphate/graphene composite material with interlay sheet structure and preparation method and application thereof |
| CN103443971B (en) * | 2011-03-25 | 2016-06-08 | 株式会社半导体能源研究所 | Lithium rechargeable battery |
| US11101460B2 (en) | 2011-03-25 | 2021-08-24 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing electrode comprising graphene layer on current collector |
| CN103443971A (en) * | 2011-03-25 | 2013-12-11 | 株式会社半导体能源研究所 | Lithium-ion secondary battery |
| US10205160B2 (en) | 2011-03-25 | 2019-02-12 | Semiconductor Energy Laboratory Co., Ltd. | Graphene composite oxide layered electrode for lithium-ion secondary batteries |
| US11799084B2 (en) | 2011-08-31 | 2023-10-24 | Semiconductor Energy Laboratory Co., Ltd. | Method for making LiFePO4 by hydrothermal method |
| US11283075B2 (en) | 2011-08-31 | 2022-03-22 | Semiconductor Energy Laboratory Co., Ltd. | Manufacturing method of composite oxide and manufacturing method of power storage device |
| US10270097B2 (en) | 2011-08-31 | 2019-04-23 | Semiconductor Energy Laboratory Co., Ltd. | Manufacturing method of composite oxide and manufacturing method of power storage device |
| TWI627129B (en) * | 2011-08-31 | 2018-06-21 | 半導體能源研究所股份有限公司 | Manufacturing method of composite oxide and manufacturing method of power storage device |
| US9556536B2 (en) | 2011-09-09 | 2017-01-31 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
| US9252419B2 (en) | 2011-09-09 | 2016-02-02 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
| CN103000862A (en) * | 2011-09-09 | 2013-03-27 | 株式会社半导体能源研究所 | Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
| US9935313B2 (en) | 2011-09-09 | 2018-04-03 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
| TWI583042B (en) * | 2011-09-09 | 2017-05-11 | 半導體能源研究所股份有限公司 | Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
| TWI557978B (en) * | 2011-09-09 | 2016-11-11 | 半導體能源研究所股份有限公司 | Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
| CN103000862B (en) * | 2011-09-09 | 2016-12-21 | 株式会社半导体能源研究所 | Positive electrode for lithium secondary battery, its manufacture method and lithium secondary battery |
| CN102332583A (en) * | 2011-10-17 | 2012-01-25 | 电子科技大学 | Method for preparing lithium iron phosphate anode material with carbon-coated surface for lithium battery |
| CN102332583B (en) * | 2011-10-17 | 2013-09-11 | 电子科技大学 | Method for preparing lithium iron phosphate anode material with carbon-coated surface for lithium battery |
| US20150102267A1 (en) * | 2012-05-14 | 2015-04-16 | Guoguang Electric Company Limited | METHOD FOR PREPARING GRAPHENE-BASED LiFePO4/C COMPOSITE MATERIAL |
| CN102683697A (en) * | 2012-05-14 | 2012-09-19 | 中南大学 | Preparation method of graphene-based LiFePO4/C composite material |
| DE112013002485B4 (en) * | 2012-05-14 | 2020-08-27 | Guoguang Electric Company Limited | Process for the production of a graphene-based LiFePO4 / C composite material |
| CN102683697B (en) * | 2012-05-14 | 2014-12-17 | 国光电器股份有限公司 | Preparation method of graphene-based LiFePO4/C composite material |
| US9672951B2 (en) * | 2012-05-14 | 2017-06-06 | Guoguang Electric Company Limited | Method for preparing graphene-based LiFePO4/C composite material |
| US10374223B2 (en) | 2013-01-23 | 2019-08-06 | Toray Industries, Inc. | Positive electrode active material/graphene composite particles, positive electrode material for lithium ion cell, and method for manufacturing positive electrode active material/graphene composite particles |
| JPWO2014115669A1 (en) * | 2013-01-23 | 2017-01-26 | 東レ株式会社 | Positive electrode active material-graphene composite particles, positive electrode material for lithium ion battery, and method for producing positive electrode active material-graphene composite particles |
| EP2950374A4 (en) * | 2013-01-23 | 2016-09-28 | Toray Industries | Positive electrode active material/graphene composite particles, positive electrode material for lithium ion cell, and method for manufacturing positive electrode active material/graphene composite particles |
| CN103346319B (en) * | 2013-07-04 | 2015-06-24 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
| CN105406035B (en) * | 2015-10-30 | 2018-03-13 | 上海应用技术学院 | A kind of preparation method of regular octahedron type ferric phosphate/graphene oxide presoma |
| CN105406035A (en) * | 2015-10-30 | 2016-03-16 | 上海应用技术学院 | Preparation method for regular octahedron-shaped iron phosphate/graphene oxide precursor |
| CN106450214A (en) * | 2016-11-08 | 2017-02-22 | 成都新柯力化工科技有限公司 | Layered lithium iron phosphate composite material and preparation method thereof |
| CN106410162A (en) * | 2016-11-15 | 2017-02-15 | 姚佑灿 | Lithium ion battery positive pole material and preparation method thereof |
| CN106602006A (en) * | 2016-11-23 | 2017-04-26 | 深圳市山木新能源科技股份有限公司 | Graphene and lithium iron phosphate composite material and preparation method thereof |
| CN107959015B (en) * | 2017-11-23 | 2018-11-16 | 江苏贝肯盛创新能源科技有限公司 | A kind of modified lithium battery positive electrode, preparation method and the lithium battery comprising it |
| CN107959015A (en) * | 2017-11-23 | 2018-04-24 | 成都新柯力化工科技有限公司 | A kind of modified lithium battery positive electrode, preparation method and include its lithium battery |
| CN108232180A (en) * | 2017-12-19 | 2018-06-29 | 刘博文 | A kind of graphene/titanium dioxide/LiFePO4 aeroge cell positive material and preparation method thereof |
| CN109301177A (en) * | 2018-08-15 | 2019-02-01 | 湖南鸿跃电池材料有限公司 | A kind of stratiform composite ferric lithium phosphate material and preparation method thereof |
| CN114512664A (en) * | 2021-12-31 | 2022-05-17 | 杭州电子科技大学 | Sandwich-structured lithium iron phosphate film/multilayer graphene composite material and preparation method thereof |
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