CN1684290A - Positive pole material for secondary lithium cell and use - Google Patents

Positive pole material for secondary lithium cell and use Download PDF

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Publication number
CN1684290A
CN1684290A CNA200410031151XA CN200410031151A CN1684290A CN 1684290 A CN1684290 A CN 1684290A CN A200410031151X A CNA200410031151X A CN A200410031151XA CN 200410031151 A CN200410031151 A CN 200410031151A CN 1684290 A CN1684290 A CN 1684290A
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China
Prior art keywords
fepo
battery
positive electrode
ions
positive
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CNA200410031151XA
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Chinese (zh)
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王德宇
陈立泉
李泓
黄学杰
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Institute of Physics of CAS
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Institute of Physics of CAS
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Priority to CNA200410031151XA priority Critical patent/CN1684290A/en
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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
    • H01M4/58—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

This invention relates to a positive material used in secondary Li cells, which is the phosphate material with the olivine structure, the formula is Lix AY Mn Nn T1/4PO4 or Mn, T is Li, Na, K, Cu, Ag, Hg and Au, M, N and T are not the same element at the same time, x, y, m,, n, t represent mol percentage. Said positive material is used in the positive of the secondary Li battery constituting a battery with conventional negative and electrolyte. In the positive material, the Li ions are replaced by some ions with the radius greater than that of the Li ions or the Fe ions are replaced by univalent metal ions to increase the electronic conductivity and ionic conductivity of the positive material in orders.

Description

A kind of positive electrode and purposes that is used for serondary lithium battery
Technical field
The present invention relates to a kind of positive electrode that is used for serondary lithium battery, specifically relate to positive electrode that a kind of serondary lithium battery uses and uses thereof with phosphate structure.
Background technology
LiFePO 4It is a kind of positive electrode active materials of novel serondary lithium battery.In 1997, J.B.Goodenough etc. apply for a patent (5,910,382, USA) propose its positive electrode as serondary lithium battery.In the same year, Armand etc. are with LiFePO 4The iron position mix and P site doped applied for patent (6,514,640, USA).LiFePO 4This class material, its advantage are that raw material is cheap, free from environmental pollution, security performance is good and theoretical capacity higher (170mAhg-1), but this conductivity of electrolyte materials is very low, causes high rate performance poor, has limited its practical application.At present, LiFePO 4It is very low to be considered to electronic conductivity, and improved method is that the carbon coating is carried out on the surface, and the high rate performance of bag material with carbon element is greatly improved, but the affiliation that adds of carbon causes the reduction of density, thereby influences the energy density of battery.(Zhaohui?Chen，and?J.R.Dahn.Reducing?Carbon?in?LiFePO 4/C?Composite?Electrodes?to?Maximize?Specific?Energy，Volumetric?Energy，and?Tap?Density.J.Electrochem.Soc.，149(9)，A1184-A1189(2002))。In addition, this method of bag carbon has only improved LiFePO 4Surface conductance, can only improve its high rate performance to a certain extent.2002, Chiang etc. proposed to adopt the way of lithium position doping high volence metal ion to improve LiFePO 4Conductivity (Sung-yoon chung, Jasont.Bloking and Yet-ming Chiang.Electronicallyconductive phospho-olivines as lithium storage electrodes.Nature material, 2,123-128 (2002)).Chiang thinks at the high volence metal ion of doping radius in lithium position less than lithium ion, can produce a large amount of rooms, therefore improves LiFePO greatly 4Electronic conductance, improved high rate performance then.But the multiplying power property of battery material is not only relevant with electronic conductance, and relevant with ionic conductance aforesaid to LiFePO 4The coating and the simple electronic conductance that improves that mixes, can not satisfy the requirement of high power lithium ion cell to high rate performance.
Summary of the invention
The objective of the invention is in order to overcome existing LiFePO 4During as the positive electrode of serondary lithium battery, the conductivity of self is low, and the doping of carbon coating and aforementioned location has also only improved the shortcoming of electronic conductance, thereby a kind of electronic conductivity and ionic conductivity that can comprehensively improve body is provided, fundamentally improves the positive electrode that is used for serondary lithium battery of the high rate performance of material.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of positive electrode that is used for serondary lithium battery, it is the phosphate material with olivine structural, and chemical formula is Li xA yM mN nT tPO 4
Wherein, A is Na, K, Ca, Cu, Ag, Hg, Au or Li;
M is Fe or Mn;
N is Ni, Mg, Co, Cu, Zn, Ti, Fe or Mn;
T is Li, Na, K, Cu, Ag, Hg, Au;
And element M, N, T are not a kind of element simultaneously;
X, y, m, n, t represents molar percentage, 0.8≤x≤1,0.001≤y≤0.2,0.7≤m≤1,0≤n≤0.3,0≤t≤0.2, and 1≤x+y≤1.05.
Use the advantage that is used for the positive electrode of serondary lithium battery provided by the invention to be: to use radius to replace lithium ion greater than some ions of lithium ion, or adopt monovalent metallic ion to replace iron ion, obtain having the phosphate material of olivine structural, the electronic conductivity of this class positive electrode and ionic conductivity all have the raising of the order of magnitude, its high rate performance also significantly improves, and demonstrates higher reversible lithium storage energy.
The invention provides a kind of above-mentioned purposes that is used for the positive electrode of serondary lithium battery, the positive electrode that this can be used for serondary lithium battery is made the positive pole of serondary lithium battery, forms serondary lithium battery with negative pole, the electrolyte of routine.The conductive additive that uses in the positive pole is carbon, conducting metal oxide or metal; But the employed active material of negative pole comprises material with carbon element, lithium transition-metal nitride or the lithium ulvospinel of lithium metal, lithium alloy removal lithium embedded; Be full of electrolyte between positive pole and the negative pole, positive pole is burn-on respectively to go between with an end of negative pole and is linked to each other with the battery case two ends of mutually insulated.
Embodiment
Embodiment 1, the preparation positive electrode Li that is used for serondary lithium battery of the present invention 0.99Na 0.01FePO 4
Phosphate positive electrode active materials Li 0.99Na 0.01FePO 4Can prepare by following steps.At first, take by weighing Li according to mol ratio 2CO 3, Na 2CO 3, FeC 2O 42H 2O and NH 4H 2PO 4, (rotating speed is 500 rev/mins, 3 hours) will change mixture at Ar-H behind the mechanical ball milling 2Gaseous mixture (Ar: H 2=92: 8; v/v) (heat treated step is: be warming up to 400 ℃ with 1 hour from room temperature to protect heat treatment down; at 400 ℃ of constant temperature after 8 hours; with dropping to room temperature in two hours); once more behind the ball milling (rotating speed is 500 rev/mins, 1 hour), mixture once more sintering (sintering step is: be warming up to 600 ℃ with 2 hours from room temperature; at 600 ℃ of constant temperature after 24 hours, with dropping to room temperature in 3 hours).
With Li 0.99Na 0.01FePO 4The anodal mixing at normal temperatures and pressures with the cyclohexane solution of acetylene black and 10% forms slurry (active material: acetylene black: PVDF=75: 15: 10), evenly is coated on the aluminum substrates, and about 2～20 μ m of the film thickness of gained are as the positive pole of simulated battery.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF 6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).Positive pole, negative pole, electrolyte are assembled into simulated battery in the glove box of argon shield.
The multiplying power testing procedure of simulated battery: at first charge to 4.5V with 30mA/g, the multiplying power current discharge is to 2.0V then, and the capacity of being emitted is the discharge capacity under this multiplying power, and discharge is discharged to 2.0V with 30mA/g after finishing again.Carry out the test of next multiplying power then.Discharging current 1C=150mA/g wherein.The test result of this simulated battery is listed in table 1.
Embodiment 2～59
Prepare the positive electrode that is used for serondary lithium battery of the present invention of various compositions by the method for embodiment 1, and make the positive pole of simulated battery.
The negative pole of simulated battery (except that embodiment 52～55), electrolyte and battery assembling are same as embodiment 1, and the composition of positive electrode and the test result of simulated battery are listed in table 1.
The negative pole of simulated battery uses MCMB as negative active core-shell material among the embodiment 52～59, electrode production process is as follows: the cyclohexane solution of negative active core-shell material MCMB, acetylene black and 5%PVDF is mixed formation slurry (active material: acetylene black: PVDF=90: 5: 5) at normal temperatures and pressures, evenly be coated on the Copper Foil substrate, about 2～the 20um of the film thickness of gained is as the negative pole of simulated battery.
The composition of table 1, positive electrode and the test result of simulated battery
Embodiment Positive electrode Discharge capacity Embodiment Positive electrode Discharge capacity
?0.2C ?1C ?10C ?30C ?0.2C ?1C ?10C ?30C
?1 ??Li 0.99Na 0.01FePO 4 ?133 ?125 ?100 ?71 31 ??Li 0.9Au 0.1Fe 0.8Co 0.2PO 4 ?128 ?112 ?88 ?62
?2 ??Li 0.999Na 0.001FePO 4 ?153 ?121 ?84 ?47 32 ??Li 0.8Na 0.2Fe 0.7Co 0.3PO 4 ?108 ?95 ?73 ?48
?3 ??Li 0.98Na 0.02FePO 4 ?129 ?120 ?99 ?73 33 ??Li 0.99Na 0.01Fe 0.99Ni 0.01PO 4 ?129 ?109 ?88 ?58
?4 ??Li 1.05FePO 4 ?145 ?133 ?106 ?81 34 ??Li 0.99Na 0.01Fe 0.8Ni 0.1Mg 0.1PO 4 ?122 ?109 ?91 ?65
?5 ??Li 0.9Na 0.1FePO 4 ?120 ?115 ?89 ?76 35 ??Li 1.02Fe 0.7Ni 0.2Co 0.1PO 4 ?109 ?98 ?85 ?62
?6 ??Li 0.8Na 0.2FePO 4 ??115 ??87 ??71 ??56 36 ??Li 0.99K 0.01Fe 0.99Cu 0.01PO 4 ??132 ?118 ?96 ?64
?7 ??Li 0.999K 0.001FePO 4 ??148 ??126 ??90 ??45 37 ??Li 0.99Ag 0.01Fe 0.9Au 0.2PO 4 ??122 ?109 ?91 ?65
?8 ??Li 0.98K 0.02FePO 4 ??135 ??126 ??99 ??78 38 ??LiFe 0.98Ag 0.04PO 4 ??138 ?125 ?96 ?75
?9 ??Li 0.8K 0.2FePO 4 ??113 ??87 ??69 ??61 39 ??Li 0.99Na 0.01Fe 0.99Zn 0.01PO 4 ??131 ?119 ?88 ?67
?10 ??Li 0.998Ca 0.002FePO 4 ??145 ??126 ??76 ??55 40 ??LiFe 0.98Hg 0.04PO 4 ??139 ?120 ?103 ?78
?11 ??Li 0.96Ca 0.04FePO 4 ??130 ??119 ??88 ??65 41 ??Li 0.8Au 0.2Fe 0.7Zn 0.3PO 4 ??98 ?87 ?65 ?51
?12 ??Li 0.8Ca 0.02FePO 4 ??105 ??83 ??54 ??21 42 ??Li 0.999Na 0.001Fe 0.99Ti 0.01PO 4 ??139 ?122 ?95 ?76
?13 ??Li 0.999Cu 0.001FePO 4 ??153 ??128 ??71 ??39 43 ??Li 0.9K 0.1Fe 0.9Ti 0.1PO 4 ??122 ?105 ?84 ?61
?14 ??Li 0.98Cu 0.02FePO 4 ??137 ??116 ??68 ??59 44 ??Li 0.99Au 0.01Fe 0.7Ti 0.3PO 4 ??110 ?86 ?73 ?51
?15 ??Li 0.8Cu 0.2FePO 4 ??118 ??89 ??73 ??58 45 ??Li 0.99Na 0.01MnPO 4 ??132 ?118 ?88 ?63
?16 ??Li 0.999Ag 0.001FePO 4 ??147 ??118 ??65 ??47 46 ??Li 0.8Ca 0.2Mn 0.8Ti 0.2PO 4 ??95 ?72 ?58 ?32
?17 ??Li 0.98Ag 0.02FePO 4 ??132 ??109 ??75 ??64 47 ??Li 0.99Cu 0.01Mn 0.99Ni 0.01PO 4 ??141 ?117 ?86 ?49
?18 ??Li 0.8Ag 0.2FePO 4 ??108 ??86 ??61 ??44 48 ??Li 0.98Cu 0.02MnPO 4 ??131 ?111 ?91 ?62
?19 ??Li 0.999Hg 0.001FePO 4 ??149 ??127 ??74 ??51 49 ??Li 0.999Na 0.001Mn 0.9Mg 0.1PO 4 ??136 ?114 ?78 ?54
?20 ??Li 0.98Hg 0.02FePO 4 ??130 ??121 ??79 ??63 50 ??Li 0.99Au 0.01Mn 0.7Co 0.3PO 4 ??98 ?77 ?55 ?36
?21 ??Li 0.8Hg 0.2FePO 4 ??105 ??88 ??57 ??46 51 ??Li 0.98K 0.02Mn 0.8Zn 0.2PO 4 ??115 ?91 ?72 ?59
?22 ??Li 0.999Au 0.001FePO 4 ??152 ??121 ??78 ??41 52 ??Li 0.99Na 0.01MnPO 4 ??117 ?89 ?68 ?52
?23 ??Li 0.98Au 0.02FePO 4 ??134 ??114 ??91 ??75 53 ??Li 0.99Na 0.01FePO 4 ??112 ?85 ?63 ?48
?24 ??Li 0.8Au 0.2FePO 4 ??111 ??92 ??61 ??49 54 ??Li 0.99K 0.01Fe 0.9Co 0.1PO 4 ??103 ?74 ?57 ?45
?25 ??Li 0.99Na 0.01Fe 0.99Mg 0.01PO 4 ??126 ??114 ??84 ??79 55 ??Li 0.99Na 0.01Fe 0.9Ni 0.1PO 4 ??97 ?72 ?60 ?51
?26 ??LiFe 0.95Na 0.1PO 4 ??128 ??119 ??100 ??81 56 ??Li 0.99Na 0.01Fe 0.95Ni 0.02Li 0.06PO 4 ??130 ?115 ?85 ?74
?27 ??LiFe 0.93Ag 0.14PO 4 ??145 ??138 ??119 ??83 57 ??Li 0.99Na 0.01Fe 0.95Cu 0.02Na 0.06PO 4 ??135 ?120 ?90 ?78
?28 ??Li 0.99K 0.01Fe 0.7Mg 0.3PO 4 ??109 ??100 ??94 ??70 58 ??Li 0.99Na 0.01Fe 0.95Mg 0.02Hg 0.06PO 4 ??145 ?130 ?100 ?75
?29 ??Li 0.98Ca 0.02Fe 0.99Co 0.01PO 4 ??133 ??121 ??99 ??70 59 ??Li 0.99Na 0.01Fe 0.9Li 0.2PO 4 ??140 ?120 ?110 ?76
?30 ??Li 0.999Au 0.001Fe 0.9Co 0.1PO 4 ??141 ??123 ??81 ??43

Claims (2)

1, a kind of positive electrode that is used for serondary lithium battery, it is the phosphate material with olivine structural, chemical formula is Li xA yM mN nT tPO 4
Wherein, A is Na, K, Ca, Cu, Ag, Hg, Au or Li;
M is Fe or Mn;
N is Ni, Mg, Co, Cu, Zn, Ti, Fe or Mn;
T is Li, Na, K, Cu, Ag, Hg, Au;
And element M, N, T are not a kind of element simultaneously;
X, y, m, n, t represents molar percentage, 0.8≤x≤1,0.001≤y≤0.2,0.7≤m≤1,0≤n≤0.3,0≤t≤0.2, and 1≤x+y≤1.05.
2, the described purposes that is used for the positive electrode of serondary lithium battery of a kind of claim 1.
CNA200410031151XA 2004-04-13 2004-04-13 Positive pole material for secondary lithium cell and use Pending CN1684290A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009053823A2 (en) 2007-10-25 2009-04-30 Toyota Jidosha Kabushiki Kaisha Positive electrode active material, lithium secondary battery, and manufacture methods therefore
WO2009092098A2 (en) 2008-01-17 2009-07-23 A123 Systems, Inc. Mixed metal olivine electrode materials for lithium ion batteries
CN101807691A (en) * 2010-04-19 2010-08-18 湘西自治州矿产与新材料技术创新服务中心 Method for preparing lithium position sodium-doped oxygen lithium vanadium phosphate anode material of lithium ion battery
WO2010139125A1 (en) * 2009-06-02 2010-12-09 Xu Ruisong Nanometer-level positive electrode material for lithium battery and method for making the same
WO2010139142A1 (en) * 2009-06-02 2010-12-09 盐光科技（嘉兴）有限公司 Positive electrode materials of secondary lithium battery and preparation methods thereof
EP2287947A1 (en) * 2008-05-22 2011-02-23 GS Yuasa International Ltd. Positive electrode active material for lithium secondary battery and lithium secondary battery
CN102044667A (en) * 2010-11-26 2011-05-04 兰州金川新材料科技股份有限公司 Method for preparing spherical LFP (lithium iron phosphate)/carbon doped composite powder
CN102511095A (en) * 2009-09-24 2012-06-20 威伦斯技术公司 Manganese phosphates and related electrode active materials
CN103474655A (en) * 2013-07-11 2013-12-25 苏州懿源宏达知识产权代理有限公司 Preparation method of potassium and manganese doped lithium iron phosphate composite anode material with high conductivity
WO2017109707A1 (en) * 2015-12-21 2017-06-29 HYDRO-QUéBEC Olivine-type compounds: method for their preparation and use in cathode materials for sodium-ion batteries

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009053823A2 (en) 2007-10-25 2009-04-30 Toyota Jidosha Kabushiki Kaisha Positive electrode active material, lithium secondary battery, and manufacture methods therefore
WO2009053823A3 (en) * 2007-10-25 2009-06-11 Toyota Motor Co Ltd Positive electrode active material, lithium secondary battery, and manufacture methods therefore
US20100203389A1 (en) * 2007-10-25 2010-08-12 Toyota Jidosha Kabushiki Kaisha Positive electrode active material, lithium secondary battery, and manufacture methods therefore
WO2009092098A2 (en) 2008-01-17 2009-07-23 A123 Systems, Inc. Mixed metal olivine electrode materials for lithium ion batteries
EP2238637A4 (en) * 2008-01-17 2016-08-03 A123 Systems Llc Mixed metal olivine electrode materials for lithium ion batteries
EP2287947A1 (en) * 2008-05-22 2011-02-23 GS Yuasa International Ltd. Positive electrode active material for lithium secondary battery and lithium secondary battery
EP2287947A4 (en) * 2008-05-22 2013-03-13 Gs Yuasa Int Ltd Positive electrode active material for lithium secondary battery and lithium secondary battery
US8431271B2 (en) 2008-05-22 2013-04-30 Gs Yuasa International Ltd. Positive active material for lithium secondary battery and lithium secondary battery
US8470207B2 (en) * 2009-06-02 2013-06-25 Ruisong Xu Nano-positive electrode material of lithium cell and method for preparation thereof
WO2010139125A1 (en) * 2009-06-02 2010-12-09 Xu Ruisong Nanometer-level positive electrode material for lithium battery and method for making the same
EP2287944A1 (en) * 2009-06-02 2011-02-23 Ruisong Xu Nanometer-level positive electrode material for lithium battery and method for making the same
EP2287944A4 (en) * 2009-06-02 2014-04-23 Ruisong Xu Nanometer-level positive electrode material for lithium battery and method for making the same
US20110114899A1 (en) * 2009-06-02 2011-05-19 Ruisong Xu Nano-Positive Electrode Material of Lithium Cell and Method for Preparation thereof
WO2010139142A1 (en) * 2009-06-02 2010-12-09 盐光科技（嘉兴）有限公司 Positive electrode materials of secondary lithium battery and preparation methods thereof
CN101567449B (en) * 2009-06-02 2012-06-27 徐瑞松 Nano-level lithium cell anodic material and preparation method thereof
CN101908624B (en) * 2009-06-02 2012-10-10 盐光科技(武汉)有限公司 Positive pole material of secondary lithium battery and preparation method thereof
RU2477908C2 (en) * 2009-06-02 2013-03-20 Жуйсун СЮЙ Nano-material of positive electrode of lithium element and method of its production
CN102511095A (en) * 2009-09-24 2012-06-20 威伦斯技术公司 Manganese phosphates and related electrode active materials
CN101807691A (en) * 2010-04-19 2010-08-18 湘西自治州矿产与新材料技术创新服务中心 Method for preparing lithium position sodium-doped oxygen lithium vanadium phosphate anode material of lithium ion battery
CN102044667A (en) * 2010-11-26 2011-05-04 兰州金川新材料科技股份有限公司 Method for preparing spherical LFP (lithium iron phosphate)/carbon doped composite powder
CN103474655A (en) * 2013-07-11 2013-12-25 苏州懿源宏达知识产权代理有限公司 Preparation method of potassium and manganese doped lithium iron phosphate composite anode material with high conductivity
CN103474655B (en) * 2013-07-11 2016-08-03 沧州锐星化学科技有限公司 A kind of preparation method of the potassium additive Mn iron phosphate compound anode material of lithium possessing high conductivity
WO2017109707A1 (en) * 2015-12-21 2017-06-29 HYDRO-QUéBEC Olivine-type compounds: method for their preparation and use in cathode materials for sodium-ion batteries
CN108698828A (en) * 2015-12-21 2018-10-23 魁北克电力公司 Olivine compounds, preparation method and the purposes in the cathode material of sodium-ion battery
JP2019503324A (en) * 2015-12-21 2019-02-07 ハイドロ−ケベック Olivine-type compounds: methods for their preparation and use in cathode materials for sodium ion batteries
JP2021119116A (en) * 2015-12-21 2021-08-12 ハイドロ−ケベック Olivine-type compounds: method for their preparation and their use in cathode materials for sodium-ion batteries
JP7094218B2 (en) 2015-12-21 2022-07-01 ハイドロ－ケベック Olivine-type compounds: methods for their preparation and use in cathode materials for sodium-ion batteries
US11569506B2 (en) 2015-12-21 2023-01-31 HYDRO-QUéBEC Olivine-type compounds: method for their preparation and use in cathode materials for sodium-ion batteries
JP7395103B2 (en) 2015-12-21 2023-12-11 ハイドロ－ケベック Olivine-type compounds: methods for their preparation and use in cathode materials for sodium-ion batteries

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