CN102610803B - Composite positive pole material for lithium ion battery and preparation method of composite material - Google Patents

Composite positive pole material for lithium ion battery and preparation method of composite material Download PDF

Info

Publication number
CN102610803B
CN102610803B CN201210083178.8A CN201210083178A CN102610803B CN 102610803 B CN102610803 B CN 102610803B CN 201210083178 A CN201210083178 A CN 201210083178A CN 102610803 B CN102610803 B CN 102610803B
Authority
CN
China
Prior art keywords
compound
lifepo
elemental sulfur
lithium ion
ion battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201210083178.8A
Other languages
Chinese (zh)
Other versions
CN102610803A (en
Inventor
王宁
窦延军
何泓材
陈海军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CN201210083178.8A priority Critical patent/CN102610803B/en
Publication of CN102610803A publication Critical patent/CN102610803A/en
Application granted granted Critical
Publication of CN102610803B publication Critical patent/CN102610803B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a composite positive pole material for a lithium ion battery, belonging to the technical field of composite functional materials. The composite positive pole material for the lithium ion battery is formed by compounding LiFePO4 as a compound with elemental sulfur, wherein LiFePO4 is a porous compound with nanometer pores; and elemental sulfur is present in the nanometer pores of LiFePO4. According to the invention, Li3PO4, FeC2O4.2H2O and (NH4)2HPO4 serve as the raw materials to prepare porous lithium iron phosphate (LiFePO4) by a hydrothermal template method; and a method of compounding gaseous sulfur with porous lithium iron phosphate is adopted to prepare the composite positive pole material. The elemental sulfur is fixed in the pores of LiFePO4, therefore, the irreversible loss of active materials caused by dissolution of the discharging product of sulfur into an electrolyte can be prevented, and the recycling performance of the positive pole material and the utilization rate of active materials can be improved. Meanwhile, the porous LiFePO4 serving as the supporting material of elemental sulfur is a good positive pole material for the lithium ion battery, and contributes to the specific capacity of the whole composite positive pole material.

Description

A kind of lithium ion battery composite cathode material and preparation method thereof
Technical field
The invention belongs to composite functional material technical field, relate to anode material for lithium-ion batteries and preparation method thereof.
Background technology
Lithium ion battery is secondary cell of new generation after lead-acid battery, ickel-cadmium cell and Ni-MH battery, have that operating voltage is high, capacity is large, self discharge is few, have extended cycle life, memory-less effect, non-environmental-pollution and the remarkable advantage such as operating temperature range is wide, as power supply renewal product, being considered to the choosing of the ideal of high power capacity, high power battery, is the environmental protection power supply of 21 century.Since coming out, be widely used in mobile phone, in the portable electric appts such as notebook computer and electric automobile, expectation is at following aerospace field, in the numerous areas such as artificial satellite and region electronics synthesis information system, jumbo lithium ion battery will be widely used aspect energy technology.As a large amount of positive electrodes that freely take off embedding/embedding lithium ion are provided, most important for the chemical properties such as operating voltage, specific energy and cycle life that improve lithium ion battery, be also the emphasis that researcher studies.At present, domestic is that researcher has the positive electrode of high voltage, high power capacity and good reversibility in active research exploitation.
The positive electrode of having commercially produced at present mainly contains LiMn2O4, lithium nickelate and cobalt acid lithium etc., and (chemical general formula is LiMO 2m=Mn, Ni or Co etc.) owing to being subject to theoretical specific capacity and raw-material restriction, having restricted it becomes desirable positive electrode, therefore, develops a kind of brand-new, high-energy-density, positive electrode pollution-free, that have outstanding cycle characteristics becomes the focus that researcher pays close attention to.
In Li-S battery, after lithium and sulphur complete reaction, generate Li 2s, its theoretical specific capacity is 1675mAh/g, and specific energy is 2600W.h/kg, and this meets the requirement of modern information technologies to chemical power source completely.Sulphur is low price as the major advantage of positive electrode, theoretical specific capacity high and with environmental friendliness etc., but there is poor cyclicity and the low problems such as active material utilization in Li-S battery, and its discharging product polysulfide is soluble in electrolyte, causes the irreversible loss of active material.Therefore, how to improve the utilance of active material, the problems of dissolution of improving many lithium sulfides becomes the subject matter that Li-S battery need to solve.Most researcher carries out the coated or metallic cover of carbon by sulphur to change the problems referred to above, the Zheng Wei of Harbin Institute of Technology is with after the coated sulphur simple substance of carbon nano-tube, its capacity can reach 700mAh/g, but because carbon and metal are the non-active ingredients in positive electrode, caused the specific capacity of cell positive material to reduce, therefore how on the basis of fixing sulphur and polysulfide, further improving material specific capacity has become a new research field again.
Another kind of anode material for lithium-ion batteries is LiFePO4, especially has the LiFePO4 (LiFePO of olivine-type one dimension tunnel structure 4) positive electrode with its raw material sources extensively, low price, nontoxic, environmentally friendly, no hygroscopicity, (3.4V is to Li for operating voltage +/ Li) typical feature such as relatively moderate is subject to researcher's extensive concern, particularly its excellent security performance and cycle performance, becomes the preferred positive electrode of lithium power energy-storage system.LiFePO 4belong to rhombic system, Pnma space group.Oxygen atom in crystal structure is arranged in the tightly packed mode of six sides of distortion a little, and phosphorus atoms occupies oxygen atom tetrahedral interstice, forms PO 4tetrahedron.Iron atom and lithium atom lay respectively at the octahedral center of oxygen atom, form FeO 6and LiO 6octahedra.One of them FeO 6octahedron respectively with two LiO 6octahedra limit altogether, and each PO 4group respectively with FeO 6octahedron and LiO 6octahedron has respectively a common edge and two common edge.Even if the LiFePO4 of this structure is under the high temperature of 400 ℃, its structure still can not become, and this has just explained electric cycle performance and the security performance that LiFePO4 system is superior to a great extent.But LiFePO 4theoretical specific capacity be about 170mAh/g, be only equivalent to the 10% more of elemental sulfur theoretical specific capacity, this makes LiFePO 4application as the positive electrode of high capacity lithium ion battery is greatly limited.
Summary of the invention
In order to improve the cyclicity of elemental sulfur positive electrode and the utilance of active material in Li-S battery, prevent that its discharging product polysulfide is dissolved in the technical problem that causes active material irreversible loss in electrolyte, the invention provides a kind of lithium ion battery composite cathode material simultaneously.This composite positive pole is composited by porous calcium phosphate iron lithium and elemental sulfur, and wherein elemental sulfur is present in the nanoscale hole of porous calcium phosphate iron lithium.The elemental sulfur that this composite positive pole can be fixed in positive electrode is polysulfide product, prevent that polysulfide is dissolved in the active material irreversible loss causing in electrolyte, elemental sulfur positive electrode more coated than existing charcoal or metallic cover has higher capacity simultaneously.The present invention provided simultaneously a kind of based on Hydrothermal Template legal system for porous calcium phosphate iron lithium, and then adopt gaseous sulfur and the mutually compound method of porous calcium phosphate iron lithium to prepare this composite positive pole.
Technical solution of the present invention is as follows:
A lithium ion battery composite cathode material, by LiFePO 4compound and elemental sulfur are composited; Wherein said LiFePO 4compound is the cellular compound with nanoscale hole, and described elemental sulfur is present in described LiFePO 4in the nanoscale hole of compound.
A preparation method for lithium ion battery composite cathode material, comprises the following steps:
Step 1: with Li 3pO 4, FeC 2o 42H 2o and (NH 4) 2hPO 4for raw material, according to Li 3pO 4: FeC 2o 42H 2o: (NH 4) 2hPO 4mol ratio carry out batch mixing, then using ethanol as dispersant, compound is carried out to ball-milling treatment;
Step 2: be dissolved in deionized water after the compound after step 1 ball-milling treatment is cleaned, is dried, then add template, and the pH value of adding Li (OH) solution regulator solution system is to neutral;
Step 3: step 2 gained solution system is placed in to high pressure water heating kettle, carries out hydro-thermal reaction in the thermal and hydric environment of 120 ℃, obtain the LiFePO that contains template 4compound;
Step 4: the LiFePO that step 3 gained is contained to template 4compound cleans and to be placed on Muffle furnace, is warming up in step 2 above the and insulation of the decomposition temperature of template used dose and processes, to remove LiFePO 4template in compound, obtains cellular LiFePO 4compound;
Step 5: by step 4 gained cellular LiFePO 4compound mixes with elemental sulfur, and is placed in tube furnace, is warming up on the fusing point of elemental sulfur, to be incubated a period of time and to make cellular LiFePO under inert gas shielding 4compound fully mixes with elemental sulfur, then continues to heat up, and makes liquid elemental sulfur vaporization and then makes gaseous elemental sulphur enter into LiFePO 4in the space of compound, finally cooling with stove, obtain final lithium ion battery composite cathode material.
The present invention utilizes Li 3pO 4, FeC 2o 42H 2o and (NH 4) 2hPO 4for raw material, based on Hydrothermal Template legal system for porous calcium phosphate iron lithium (LiFePO 4), and then adopt the mutually compound method of gaseous sulfur and porous calcium phosphate iron lithium to prepare this composite positive pole.It should be noted that, in step 2, template used dose can be CTAB (softex kw), SDS (lauryl sodium sulfate), P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polyether) or F127 (EO-PO type polyethers).Use different templates, can obtain the porous LiFePO of different pore size 4, the consumption of different templates agent can obtain the porous LiFePO of different porosities 4.Cellular LiFePO in step 5 4when compound mixes with elemental sulfur, should use excessive elemental sulfur, gaseous elemental sulphur enters cellular LiFePO 4in the space of compound and by nanoscale space, fix, unnecessary sulphur can be pulled away along with flowing of tube furnace inert gas; Certainly, the cellular LiFePO finally obtaining 4the lithium ion anode material that compound and elemental sulfur are compound, has a little elemental sulfur and is attached to LiFePO 4compound surface, but this does not affect the application of this positive electrode in lithium ion battery, (lithium ion battery that utilizes this positive electrode to make positive plate and then be assembled into, in charge and discharge process in the early stage, is attached to LiFePO 4a little elemental sulfur on compound surface can lose, and then causes the decline of positive electrode specific capacity, but along with discharging and recharging the increase of number of times, the specific capacity of this positive electrode can settle out very soon).
Lithium ion battery composite cathode material provided by the invention is in fact to utilize cellular LiFePO 4compound carries out " being coated " to elemental sulfur, and (so-called " being coated " refers to that elemental sulfur enters into LiFePO here 4in the hole of compound, utilize LiFePO 4the hole of compound is fixed elemental sulfur, but sulphur still can contact with the electrolyte that infiltration is come in, and produces embedding and the de-embedding of lithium ion, but lithium ion while embedding the polysulfide of generation due to the restriction of nanoscale hole, can not enter into electrolyte).Because elemental sulfur is well secured to LiFePO 4in the hole of compound, the positive plate that utilizes this positive electrode to make is assembled into after lithium ion battery, can prevent that thereby its discharging product polysulfide is dissolved in the irreversible loss that causes active material in electrolyte, and then improve the cyclicity of sulphur positive electrode and the utilance of active material.Meanwhile, as the backing material cellular LiFePO of elemental sulfur 4compound, itself is also a kind of good anode material for lithium-ion batteries, and the specific capacity of whole composite positive pole is also had to certain contribution (being compared to the elemental sulfur positive electrode of the coated or metallic cover of charcoal).
Embodiment
Embodiment 1
A lithium ion battery composite cathode material, by LiFePO 4compound and elemental sulfur are composited; Wherein said LiFePO 4compound is the cellular compound with nanoscale hole, and described elemental sulfur is present in described LiFePO 4in the nanoscale hole of compound.Wherein, containing elemental sulfur 20wt%, all the other are cellular LiFePO 4compound.
The preparation process of above-mentioned lithium ion battery composite cathode material is:
1 weighs Li according to stoichiometric proportion at 1: 3: 3 3pO 4, FeC 2o 42H 2o and (NH 4) 2hPO 4, after mixing, using ethanol as dispersant, on planetary ball mill, ball milling is 4 hours, and rotating speed is 400rpm.
2 clean above-mentioned ball milling product respectively 5 times with deionized water and ethanol, then at 90 ℃, are dried.
3 join 2.5g template CTAB in 100ml deionized water, then products therefrom weighing 4g in second step is put into this deionized water, finally splash into Li (OH) solution regulator solution system to neutral.
4 put into reactor by configured solution, and the environment that is placed in 120 ℃ keeps 4 hours.
5 by hydrothermal product washing 5 times, and ethanol is washed 5 times.
6 put into Muffle furnace in 550 ℃ of maintenances 6 hours by upper step products therefrom, and products therefrom is cellular LiFePO 4compound.
7 by cellular LiFePO 4compound and elemental sulfur are put into the tube furnace that is connected with nitrogen by the mass ratio of 1: 5, keep 8 hours at 150 ℃, keep 4 hours at 350 ℃, then naturally cooling, and products therefrom is mesoporous LiFePO4+sulphur composite positive pole.
Outward appearance: black powder, particle is tiny.By TEM transmission electron microscope observing microstructure, hole diameter is approximately 2.3nm, has good uniformity.
Material property: by above-mentioned positive electrode and acetylene black, PVDF is made into positive plate in 8: 1: 1 ratios, finally with the positive plate preparing, carry out the assembling of button cell, finally by LAND battery test system, the battery assembling is tested, result shows that this battery first discharge specific capacity can reach 1100mAh/g, after 20 circulations, Capacitance reserve is in 950mAh/g left and right, this illustrates that mesoporous LiFePO4 has good covered effect to sulphur and discharging product polysulfide thereof, prevented that polysulfide from dissolving in electrolyte, the cycle characteristics of battery has been had to good improvement.
Embodiment 2
Concrete steps are same as Example 1, and that difference is that template selects use is SDS.
Composite positive pole: containing elemental sulfur 27wt%, all the other are cellular LiFePO 4compound (template is SDS).
Appearance property: black powder, particle is tiny.By TEM transmission electron microscope observing microstructure, hole diameter is approximately 3.4nm, has good uniformity.
Material property: by above-mentioned positive electrode and acetylene black, PVDF is made into positive plate in 8: 1: 1 ratios, finally with the positive plate preparing, carry out the assembling of button cell, finally by LAND battery test system, the battery assembling is tested, result shows that this battery first discharge specific capacity can reach 1052mAh/g, after 20 circulations, Capacitance reserve is in 920mAh/g left and right, this illustrates that mesoporous LiFePO4 has good covered effect to sulphur and discharging product polysulfide thereof, prevented that polysulfide from dissolving in electrolyte, the cycle characteristics of battery has been had to good improvement.
Embodiment 3
Concrete steps are same as Example 1, and that difference is that template selects use is P123.
Composite positive pole: containing elemental sulfur 35wt%, all the other are cellular LiFePO 4compound (template is P123).
Appearance property: black powder, particle is tiny.By TEM transmission electron microscope observing microstructure, hole diameter is approximately 5.1nm, has good uniformity.
Material property: by above-mentioned positive electrode and acetylene black, PVDF is made into positive plate in 8: 1: 1 ratios, finally with the positive plate preparing, carry out the assembling of button cell, finally by LAND battery test system, the battery assembling is tested, result shows that this battery first discharge specific capacity can reach 916mAh/g, after 20 circulations, Capacitance reserve is in 886mAh/g left and right, this illustrates that mesoporous LiFePO4 has good covered effect to sulphur and discharging product polysulfide thereof, prevented that polysulfide from dissolving in electrolyte, the cycle characteristics of battery has been had to good improvement.
Embodiment 4
Concrete steps are same as Example 1, and that difference is that template selects use is F127.
Composite positive pole: containing elemental sulfur 50wt%, all the other are cellular LiFePO 4compound (template is F127)
Appearance property: black powder, particle is tiny.By TEM transmission electron microscope observing microstructure, hole diameter is approximately 7.5nm, has good uniformity.
Material property: by above-mentioned positive electrode and acetylene black, PVDF is made into positive plate in 8: 1: 1 ratios, finally with the positive plate preparing, carry out the assembling of button cell, finally by LAND battery test system, the battery assembling is tested, result shows that this battery first discharge specific capacity can reach 906mAh/g, after 20 circulations, Capacitance reserve is in 800mAh/g left and right, this illustrates that mesoporous LiFePO4 has good covered effect to sulphur and discharging product polysulfide thereof, prevented that polysulfide from dissolving in electrolyte, the cycle characteristics of battery has been had to good improvement.

Claims (2)

1. a preparation method for lithium ion battery composite cathode material, comprises the following steps:
Step 1: with Li 3pO 4, FeC 2o 42H 2o and (NH 4) 2hPO 4for raw material, according to Li 3pO 4: FeC 2o 42H 2o:(NH 4) 2hPO 4the mol ratio of=1:3:3 is carried out batch mixing, then usings ethanol as dispersant, and compound is carried out to ball-milling treatment;
Step 2: be dissolved in deionized water after the compound after step 1 ball-milling treatment is cleaned, is dried, then add template, and add Li(OH) the pH value of solution regulator solution system is to neutral;
Step 3: step 2 gained solution system is placed in to high pressure water heating kettle, carries out hydro-thermal reaction in the thermal and hydric environment of 120 ℃, obtain the LiFePO that contains template 4compound;
Step 4: the LiFePO that step 3 gained is contained to template 4compound cleans and to be placed on Muffle furnace, is warming up in step 2 above the and insulation of the decomposition temperature of template used dose and processes, to remove LiFePO 4template in compound, obtains cellular LiFePO 4compound;
Step 5: by step 4 gained cellular LiFePO 4compound mixes with elemental sulfur, and is placed in tube furnace, is warming up on the fusing point of elemental sulfur, to be incubated a period of time and to make cellular LiFePO under inert gas shielding 4compound fully mixes with elemental sulfur, then continues to heat up, and makes liquid elemental sulfur vaporization and then makes gaseous elemental sulphur enter into LiFePO 4in the space of compound, finally cooling with stove, obtain final lithium ion battery composite cathode material.
2. the preparation method of lithium ion battery composite cathode material according to claim 1, is characterized in that, in step 2, template used dose is CTAB, SDS, P123 or F127.
CN201210083178.8A 2012-03-27 2012-03-27 Composite positive pole material for lithium ion battery and preparation method of composite material Expired - Fee Related CN102610803B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210083178.8A CN102610803B (en) 2012-03-27 2012-03-27 Composite positive pole material for lithium ion battery and preparation method of composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210083178.8A CN102610803B (en) 2012-03-27 2012-03-27 Composite positive pole material for lithium ion battery and preparation method of composite material

Publications (2)

Publication Number Publication Date
CN102610803A CN102610803A (en) 2012-07-25
CN102610803B true CN102610803B (en) 2014-04-09

Family

ID=46528044

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210083178.8A Expired - Fee Related CN102610803B (en) 2012-03-27 2012-03-27 Composite positive pole material for lithium ion battery and preparation method of composite material

Country Status (1)

Country Link
CN (1) CN102610803B (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140370388A1 (en) * 2013-06-18 2014-12-18 Seeo, Inc. Method for determining state of charge in lithium batteries through use of a novel electrode
CN103441282B (en) * 2013-08-09 2015-06-24 华南师范大学 LiMnPO4/C lithium ion battery anode material prepared by template method and preparation method of anode material
CN106876699A (en) * 2015-12-13 2017-06-20 中国科学院大连化学物理研究所 A kind of combination electrode and its preparation and application
CN106410194A (en) * 2016-11-25 2017-02-15 上海空间电源研究所 Composite lithium battery and preparation method thereof
CN109088043A (en) * 2017-06-14 2018-12-25 中南大学 A kind of lithium sulphur-lithium ion hybrid battery and lithium sulphur-lithium ion hybrid battery positive electrode and preparation method thereof
CN109167034B (en) * 2018-08-21 2021-07-23 南开大学 Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof
CN111224103A (en) * 2020-01-17 2020-06-02 贝特瑞（天津）纳米材料制造有限公司 Preparation method of metal ion-doped high-rate mesoporous lithium iron phosphate cathode material
CN111342011B (en) * 2020-03-02 2021-07-06 沁新集团(天津)新能源技术研究院有限公司 Lithium iron phosphate/sulfur carbon composite cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery
CN113991120B (en) * 2021-12-27 2022-03-22 湖南长远锂科股份有限公司 Lithium iron phosphate anode material and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101384630B1 (en) * 2008-03-12 2014-04-11 유니버시티 오브 워터루 Sulfur-carbon material
IN2012DN02063A (en) * 2009-08-28 2015-08-21 Sion Power Corp

Also Published As

Publication number Publication date
CN102610803A (en) 2012-07-25

Similar Documents

Publication Publication Date Title
CN102610803B (en) Composite positive pole material for lithium ion battery and preparation method of composite material
CN102569797B (en) Novel phosphate based composite cathode material, its preparation method and application thereof
Yuan et al. Synthesis of Li3V2 (PO4) 3 cathode material via a fast sol–gel method based on spontaneous chemical reactions
Wang et al. Enhanced electrochemical performance of unique morphological LiMnPO4/C cathode material prepared by solvothermal method
CN101964411B (en) LiFePO4 composite type positive pole material preparation method
CN112420999B (en) Phosphorus-based negative electrode material with coating structure and preparation method and application thereof
TW200805734A (en) The preparation and application of the LiFePO4/Li3V2(PO4)3 composite cathode materials for lithium ion batteries
CN103165883B (en) Lithium ion battery phosphate anode composite material and its production and use
Zhao et al. Effects of neodymium aliovalent substitution on the structure and electrochemical performance of LiFePO4
CN103384001B (en) A kind of graphene combination electrode material and solid catalysis preparation method thereof
CN103779564A (en) High-performance sodium vanadyl phosphate symmetrical sodium-ion battery material and preparation method and application thereof
CN102299332B (en) Preparation method of porous lithium vanadium phosphate/carbon cathode material of lithium ion battery
Hsieh et al. Green chemical delithiation of lithium iron phosphate for energy storage application
Oh et al. Electrochemical properties of Li3-xNaxV2-xTix (PO4) 3/C cathode materials in lithium ion batteries
CN103996852A (en) Preparation method of novel nano lithium vanadium phosphate positive electrode material
CN102024989A (en) Preparation method of high-voltage lithium-ion battery
Li et al. High-performance Na3V2 (PO4) 2F2. 5O0. 5 cathode: Hybrid reaction mechanism study via ex-situ XRD and sodium storage properties in solid-state batteries
Alfaruqi et al. Carbon-coated rhombohedral Li2NaV2 (PO4) 3 nanoflake cathode for Li-ion battery with excellent cycleability and rate capability
Wang et al. Sustainable synthesis of Ni, Mn co-doped FePO4@ C cathode material for Na-ion batteries
CN101118963A (en) Method for preparing anode material iron phosphate lithium of lithium ion battery
Du et al. A three volt lithium ion battery with LiCoPO4 and zero-strain Li4Ti5O12 as insertion material
Xu et al. The effect of NiO as graphitization catalyst on the structure and electrochemical performance of LiFePO4/C cathode materials
CN103956491A (en) Lithium ion battery anode material manganese lithium iron phosphate and preparation method thereof
CN107123802A (en) A kind of preparation method of graphene modified phosphate iron lithium material
CN103633326B (en) The production method of LiFePO4

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140409

Termination date: 20180327