CN101540398A - Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof - Google Patents
Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof Download PDFInfo
- Publication number
- CN101540398A CN101540398A CN200810102098A CN200810102098A CN101540398A CN 101540398 A CN101540398 A CN 101540398A CN 200810102098 A CN200810102098 A CN 200810102098A CN 200810102098 A CN200810102098 A CN 200810102098A CN 101540398 A CN101540398 A CN 101540398A
- Authority
- CN
- China
- Prior art keywords
- meso
- transition metal
- hole structure
- olivine
- preparation
- 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.)
- Pending
Links
Images
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)
Abstract
The invention relates to a phosphate material having a mesoporous structure for lithium secondary batteries and a preparation method thereof. The material having a mesoporous structure is secondary particles which have a mesoporous spherical or spheroid shape and are formed by the agglomeration of primary particles; the chemical composition of the material having the mesoporous structure is represented by the formula of LixAaMmBbPOzNn; the average particle diameter of the primary particles is 10nm to 1mum, the average particle diameter of the secondary particles is 100nm to 50mum, the average pore diameter of mesopores is 2 to 500nm; and the material having the mesoporous structure also comprises a layer of 2 to 100nm thick carbon coated outside the secondary particles and on the inner walls of the mesopores, wherein the content of the carbon accounts for 1 to 20 weight percent of the total weight of a substrate. The material is prepared by the steps of: firstly preparing pure-phase phosphate LiMPO4 or doped LiMPO4 sol; secondly, forming dry gel through heat treatment; and finally, forming the agglomerate secondary particles through sintering at high temperature. The phosphate material having the mesoporous structure can be directly used in secondary lithium batteries as an anode active material and can also be used by being mixed with the prior anode material as an additive. The material having the mesoporous structure can improve the rate performance and energy density of the prior anode material and batteries. The secondary lithium batteries containing the phosphate material having the mesoporous structure has high power density and high safety.
Description
Technical field
The present invention relates to a kind of positive electrode that is used for serondary lithium battery, specifically relate to a kind of olivine that serondary lithium battery uses or NASICON type lithium transition metal phosphates positive electrode and preparation method thereof of being used for meso-hole structure.
Background technology
At United States Patent (USP) 5,871, NASICON type phosphate material Li3V2 (PO4) 3 application as positive pole material of secondary lithium battery at first proposed in 866 at J.Barker in 1996 etc.J.B.Goodenough in 1997 etc. propose in U.S. Pat A 5,910,382, with the positive electrode of LiFePO4 as serondary lithium battery.In the same year, M.Armand etc. are at U.S. Pat A6, disclose in 514,640 LiFePO4 is carried out the material that mix in the iron position and phosphate potential is alternative.It is cheap that this class material of LiFePO4, its major advantage are that this class material has the prices of raw and semifnished materials, and storage is abundant, environmentally safe, and chemical property is stable, and when serondary lithium battery was used, security performance was very good, and lithium storage content is higher, and voltage is than characteristics such as height.But this class material also exists electronic conductance and the low shortcoming of ionic conductivity.As the positive electrode active materials of serondary lithium battery, the multiplying power property of battery is relatively poor.That is to say that battery is when high current charge-discharge, battery capacity obviously reduces (for example, less than 70%) when charging and discharging with respect to little electric current.In order to address these problems, often adopt the granularity reduce phosphate material and improve electrical contact performance between the particle in the method for its coated with carbon or plated metal, reduce to add more binding agent when the coating of particle and carbon makes the manufacturing pole piece, influence the conductivity of pole piece, also make the density of pole piece and the activity substance content of unit volume reduce significantly.So just be unfavorable for producing the battery of high-energy-density.Though Chinese patent 200510094812.8 discloses the spherical porous preparation methods of a kind of spherical LiFePO4; adopt the method for two step coprecipitation synthesizing iron lithium phosphate presomas; earlier synthetic ferrous phosphate; synthetic with step precipitation method again to its coating lithium phosphate; calcine synthesizing iron lithium phosphate down by protective atmosphere again; this method can not be synthesized the material with meso-hole structure; because it is very little for the contribution of ion transfer to contain semiclosed hole less than the micropore of 2nm, mesoporous size is not described in the patent yet.Chinese patent 200710072533.0 discloses a kind of LiFePO4/C composite material with honeycomb, also be to adopt coprecipitation, earlier synthetic NH4FePO4H2O, again and lithium carbonate, glucose etc. are mixed with the composite material of LiFePO4 and carbon, can not form material with meso-hole structure, and this material can not overcome the low density shortcoming of pole piece equally, carbon coated content acquires a certain degree the back to the material electrochemical performance influence not quite, adopt the method for solid-phase sintering can make the skewness that forms carbon, and easy reunion of LiFePO4 cause local conductivity bad.High rate performance when these all can influence it as positive pole material of secondary lithium battery.
Summary of the invention
It is poor to the objective of the invention is when overcoming existing LiMPO4 class material as the positive electrode of serondary lithium battery multiplying power property, and makes the low density shortcoming of pole piece.Thereby provide a kind of olivine of the meso-hole structure with quick ion transfer passage and high-tap density or sodium fast-ionic conductor (hereinafter to be referred as " NASICON "; List of references: J.B.Goodenough, H.Y.P.Hong, J.A.Kafalas, Mater.Res.Bull.11. (1976) 203) type lithium transition metal phosphates material; And provide a kind of preparation to be used for the method for the phosphate material having mesoporous structure of lithium secondary battery.
The object of the present invention is achieved like this:
Olivine or sodium fast-ionic conductor type lithium transition metal phosphates material with meso-hole structure provided by the invention, it is characterized in that, this mesoporous material is the primary particle of the LiMPO4 of the pure phase LiMPO4 of 10nm～1um or doping by average grain diameter, form second particle through reuniting again, form mesoporous between the described primary particle with nanoscale mesopore orbit;
The chemical composition of the LiMPO4 of described doping is represented with following formula:
LixAaMmBbPOzNn
Wherein, in described pure phase LiMPO4 or the LixAaMmBbPOzNn formula, A is Na, Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In or Ge;
M is Fe, Co, Mn, Ni or V;
B is Li, Na, K, Ca, Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In or Ge;
And M and B are not with a kind of element simultaneously;
X, a, m, b, z, n represents molar percentage, 0.9≤x≤1.8; 0≤a≤0.1; 0.5≤m≤1; 0≤b≤0.5; 3≤z≤4; 0≤n≤1.
In above-mentioned technical scheme, also being included in the surperficial or mesoporous inwall deposition of described mesoporous material second particle coating one layer thickness is the carbon film of 2～100nm, the content of carbon accounts for 1～20wt% of mesoporous material weight, the thickness of preferred carbon coating layer is 2～20nm, and the content of carbon accounts for 1～5wt% of mesoporous material weight.
In above-mentioned technical scheme, the geometric shape of described second particle can be sphere or elliposoidal, and average grain diameter is 100nm～50um.Be preferably 500m～30um.
In above-mentioned technical scheme, described mesoporous average pore size is 2～500nm, is preferably 10～200nm; Described nanoscale mesopore orbit can be to connect continuously or the partial continuous perforation.
The present invention also provides the olivine that a kind of preparation has meso-hole structure or the method for sodium fast-ionic conductor type lithium transition metal phosphates material, it is characterized in that, may further comprise the steps:
1) preparation of colloidal sol: the preparation of the colloidal sol of pure phase phosphate LiMPO4 is with lithium salts, transition metal salt and phosphoric acid, be in molar ratio (1～1.1): 1: (1～1.05) adds in the solvent, stirred 0.5～1.5 hour, forming concentration is the homogeneous solution of 0.01-2 mole, adds NH4H2O again and regulate the pH value of this solution until continuing after 6～8 to stir till forming colloidal sol in this solution;
1 ') preparation of doped meso-porous structure phosphate LixAaMmBbPOzNn colloidal sol: be in above-mentioned steps 1) the colloidal sol preparation process in, add transition metal salt a kind of of the corresponding element of pressing the chemical dosage ratio among the chemical formula LixAaMmBbPOzNn;
Metal A is: Na, and Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In, Ge,
Metal M is Fe, Co, Mn, Ni or V
Metal B is Li, Na, K, Ca, Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In, Ge; And M and B are not with a kind of element simultaneously;
X, a, m, b, z, n represents molar percentage, 0.9≤x≤1.8; 0≤a≤0.1; 0.5≤m≤1; 0≤b≤0.5; 3≤z≤4; 0≤n≤1;
2) heat-treat the formation xerogel: described colloidal sol is heat-treated under inert atmosphere protections such as air or Ar, N2, heat treatment temperature is between 60 ℃-200 ℃, heating is until with the solvent evaporate to dryness, thereby obtains the predecessor of phosphate material having mesoporous structure, i.e. xerogel; Heating process can be carried out under air, if but oxidation can take place in selected transition metal salt under this heating-up temperature, and then heating process is carried out under high-purity Ar or N2 gas shiled;
3) high temperature sintering: with step 2) xerogel that obtains carries out solid-phase sintering in air, for oxidation takes place when the sintering in the anti-selected transition metal salt of oxidation, then with xerogel in high-purity Ar, carry out sintering in N2 or the Ar/H2 gaseous mixture;
Described sintering temperature is between 400 ℃～900 ℃, sintering time is 3～48 hours, natural cooling obtains the micron order olivine with meso-hole structure that is made of the nanoscale primary particle or the second particle of NASICON type lithium transition-metal material, the spherical in shape or elliposoidal of this particle then.
In above-mentioned technical scheme, also be included in and carry out carbon vapour deposition cladding process on this second particle again, to form the nanoscale carbon-coating, perhaps directly mix positive electrode as serondary lithium battery with nano grade carbon black on a ball surface that exposes; The preparation technology of described coated with carbon is a common process, for example according to list of references 1:J.Electrochem.Soc., 149 (9), the technology of A1184-A1189 (2002) is carried out, be behind the LiMPO4 for preparing pure phase or doping, chemical vapour deposition (CVD) on its surface by routine, methods such as solid-phase sintering coat carbon-coating, or use liquid phase to coat the method for carbon-coating, promptly in the process of synthesising mesoporous structure phosphate material colloidal sol, add carbon matrix precursor, form carbon coating layer during again by solid-phase sintering.
In above-mentioned technical scheme, described lithium salts comprises lithium acetate, lithium citrate, lithium nitrate or lithium oxalate.
In above-mentioned technical scheme, described transition metal salt comprises: acetate, citrate, nitrate or oxalates.
In above-mentioned technical scheme, the solvent that uses in the described step 1) comprises: ethylene glycol, ethanol, methyl alcohol, glycerol, isopropyl alcohol or polyethylene glycol, or ethylene glycol, glycerol, two or more mixing in isopropyl alcohol or the polyethylene glycol.
The serondary lithium battery that phosphate material having mesoporous structure provided by the invention is made is applicable to that various mobile electronic devices maybe need the equipment of mobile driven by energy, mobile phone for example, notebook computer, portable video recorder, electronic toy, high power electrokinetic cell particularly, as be used in electric tool, electric automobile, hybrid vehicle, electric topedo, fields such as accumulation power supply, and be not limited to this.
The advantage of meso-hole structure olivine provided by the invention or NASICON type lithium transition metal phosphates material is:
1) the present invention has prepared the LiMPO4 with mesoporous pure phase, the LiMPO4 of doping or the meso-hole structure material of the LiMPO4 of coated with carbon; This material has improved the high rate performance of existing phosphate material battery significantly, the secondary spherical pure phase LiFePO4 of the 2um that forms by the primary particle that is of a size of 200nm during with the 10C multiplying power discharging capacity can reach 95mAh/g; The serondary lithium battery that contains this meso-hole structure material has the big remarkable advantage of power density.
2) meso-hole structure material provided by the invention, secondary ball with bigger size, can reduce the consumption of binding agent in the pole piece manufacture process significantly, improve activity substance content in the unit volume pole piece, the binding agent consumption is reduced to 3wt% by the 8wt% of proprietary concentrate.
3) because in this meso-hole structure material provided by the invention, has the nanoscale duct that continuous perforation or partial continuous connect, thereby electrolyte solution can infiltrate these nanoscale ducts fully to be contacted with electrode material, the passage that can transport fast for ion so just is provided and has had a big reaction interface (J.Power Sources, 153,274-280 (2006)), overcome olivine or NASICON section bar material interface transport property difference and the slow shortcoming of interfacial reaction, helped improving the high rate performance of battery.
4) because in this meso-hole structure material provided by the invention, can on spheric granules surface or granule interior cell walls, coat one deck carbon film, can whole second particle overlap joint be formed continuous uniform conductive network by this layer conductive carbon film, therefore can keep good electrical contact by a direct sum active material.
5) meso-hole structure material provided by the invention can form a favorable conductive network behind the carbon film in the coating.Mix use with it or as conductive additive with other positive electrode, can improve the multiplying power of existing positive electrode and battery when being used for serondary lithium battery, have the big remarkable advantage that waits of power density.In addition, because the material, the particularly material of LiFePO4 class of olivine structural have good fail safe, can also improve the security performance of other positive electrode.
6) preparation method's technology of the present invention is simple, by directly pre-reaction material being dissolved in the organic solvent, control heat treatment temperature and heat treatment time just can be prepared has the micron order olivine with meso-hole structure that is made of the nanoscale primary particle or the secondary ball of NASICON type lithium transition-metal material.
Description of drawings
Below, describe embodiments of the invention in conjunction with the accompanying drawings in detail, wherein:
Fig. 1 is the meso-hole structure pure phase LiFePO4 stereoscan photograph of embodiment 1 preparation;
Fig. 2 is the meso-hole structure pure phase LiFePO4 stereoscan photograph of embodiment 1 preparation;
Fig. 3 is the meso-hole structure pure phase LiCoPO4 stereoscan photograph of embodiment 2 preparations;
Fig. 4 is the meso-hole structure pure phase LiCoPO4 stereoscan photograph of embodiment 2 preparations.
Embodiment
Embodiment 1, the preparation meso-hole structure pure phase LiFePO4 that is used for serondary lithium battery of the present invention, prepared this sample reference as attached Fig. 1 and 2.
The meso-hole structure pure phase LiFePO4 of present embodiment can prepare by following steps.At first; take by weighing the LiAc2H2O of 1.02g respectively; 2.48g Fe (Ac) 24H2O and the H3PO4 of 0.98g; add and fill in the beaker of 200ml ethylene glycol; use magnetic stirrer extremely evenly to disperse in 30 minutes; add NH4H2O and regulate the pH value to 7-8; continue magnetic agitation 0.5 hour to forming colloidal sol; this colloidal sol is heat-treated in high-purity Ar gas (heat treatment step is: with colloidal sol 120 ℃ the heating 3 hours; be warming up to 140 ℃ then until becoming xerogel); xerogel is carried out sintering under the high-purity Ar gas shiled (sintering step is: be warming up to 700 ℃ with 3 hours from room temperature; at 700 ℃ of constant temperature after 12 hours, 5 hours cool to room temperature again).The stereoscan photograph of the LiFePO4 sample of gained is shown in attached Fig. 1 and 2, and the mesoporous LiFePO4 shown in attached Fig. 1 and 2 is spherical, and the primary particle average grain diameter is 200nm, and the second particle average grain diameter is 2um, and mesoporous average pore size is 80nm.
The LiFePO4 material of the meso-hole structure that present embodiment is made mixes formation slurry (active material: acetylene black: PVDF=92: 5: 3) at normal temperatures and pressures with the n-formyl sarcolysine base pyrrolidone solution of acetylene black and 3% Kynoar (PVDF), evenly be coated on the aluminum substrates, then 100 ℃ of vacuumizes after 5 hours, the film of gained is compressed under 10MPa pressure, the about 100 μ m of the film thickness of gained are cut into the positive pole of the electrode slice of 1x1cm as simulated battery.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is dissolved in for 1mol LiPF6 in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery: at first charge to 4.2V with 30mA/g, the multiplying power current discharge is to 2.5V then, the capacity of being emitted reaches 145mAh/g with the Mass Calculation of mesoporous LiFePO4, when discharging current increases to 1500mA/g, the discharge capacity of this material is 95mAh/g, this current density is equivalent to the charge-discharge magnification of 10C, and this result shows that mesoporous LiFePO4 has high-multiplying power discharge characteristic preferably.
Embodiment 2, the preparation mesoporous positive electrode LiCoPO4 that is used for serondary lithium battery of the present invention.This prepared sample reference is as accompanying drawing 3 and 4.
Mesoporous positive electrode LiCoPO4 can prepare by following steps.At first, take by weighing the LiAc2H2O of 1.05g respectively, 2.51g Co (Ac) 24H2O and the H3PO4 of 0.98g, add and fill in the beaker of 80ml ethylene glycol, use magnetic stirrer extremely evenly to disperse in 30 minutes, add NH4H2O and regulate pH value to 7～8, continue magnetic agitation 0.5 hour to forming colloidal sol, this colloidal sol is heat-treated in air (heat treatment step is: with colloidal sol 120 ℃ the heating 1 hour, be warming up to 140 ℃ then until becoming xerogel), xerogel is carried out sintering (sintering step is: be warming up to 700 ℃ with 3 hours from room temperature, at 700 ℃ of constant temperature after 12 hours, 5 hours cool to room temperature again) under air.The stereoscan photograph of the LiCoPO4 sample of gained as shown in Figure 3, the mesoporous LiCoPO4 shown in the accompanying drawing 3 and 4 is spherical, the primary particle average grain diameter is 400nm, the second particle average grain diameter is 3um, mesoporous average pore size is 60nm.
The anodal mixing at normal temperatures and pressures with the n-formyl sarcolysine base pyrrolidone solution of acetylene black and 3% Kynoar (PVDF) of the LiCoPO4 of meso-hole structure formed slurry (active material: acetylene black: PVDF=92: 5: 3), evenly be coated on the aluminum substrates, then 100 ℃ of vacuumizes after 5 hours, the film of gained is compressed under 10MPa pressure, the about 100 μ m of the film thickness of gained are cut into the positive pole of the electrode slice of 1x1cm as simulated battery.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is dissolved in for 1mol LiPF6 in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery: at first charge to 5V with 30mA/g, the multiplying power current discharge is to 2.5V then, the capacity of being emitted reaches 120mAh/g with the Mass Calculation of mesoporous LiCoPO4, and when discharging current increased to 1500mA/g, the discharge capacity of this material was 50mAh/g.
Embodiment 3, meso-hole structure doped iron lithium phosphate material
Doped iron lithium phosphate Li0.99Na0.01FePO4 can prepare by following steps.At first; take by weighing the LiAc2H2O of 1.02g respectively; 2.46g Fe (Ac) 24H2O; 0.035g NaAc3H2O and the H3PO4 of 0.98g; add and fill in the beaker of 50ml ethylene glycol; use magnetic stirrer extremely evenly to disperse in 1 hour; add NH4H2O and regulate pH value to 7～8; continue magnetic agitation 1.5 hours to forming colloidal sol; this colloidal sol is heat-treated in high-purity Ar gas (heat treatment step was: with 150 ℃ of colloidal sols heating 5 hours; be warming up to 170 ℃ then until becoming xerogel); xerogel is carried out sintering under the high-purity Ar gas shiled (sintering step is: be warming up to 700 ℃ with 2 hours from room temperature; at 700 ℃ of constant temperature after 12 hours, 3 hours cool to room temperature again).The meso-hole structure Li0.99Na0.01FePO4 primary particle average grain diameter of gained is 200nm, and the second particle average grain diameter is 10um, and mesoporous average pore size is 80nm.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is that the LiPF6 of 1mol is dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery: at first charge to 4.2V with 30mA/g, the multiplying power current discharge is to 2.5V then, the capacity of being emitted reaches 145mAh/g with meso-hole structure doped iron lithium phosphate material 3 Mass Calculation, when discharging current increases to 1500mA/g, the discharge capacity of this material is 110mAh/g, and this this result shows that meso-hole structure doped iron lithium phosphate material 3 has high-multiplying power discharge characteristic preferably.
Embodiment 4, meso-hole structure nitrogen doped iron lithium phosphate material
Nitrogen doped iron phosphate lithium anode material Li1.1Fe0.9PO3.9N0.1 can prepare by following steps.At first, take by weighing the H3PO4 of the LiAc2H2O of 1.402g, the Fe of 2.790g (Ac) 24H2O and 1.225g respectively, add and fill in the beaker of 100ml ethylene glycol, use magnetic stirrer extremely evenly to disperse in 0.5 hour, add NH4H2O and regulate the pH value to 7-8, the continuation magnetic agitation was heat-treated this colloidal sol (heat treatment step is: with 100 ℃ of heating of colloidal sol 5 hours, be warming up to 120 ℃ then until becoming xerogel) to forming colloidal sol in 3 hours in high-purity N 2 gas.With this mixture in ammonia nitrogen gaseous mixture (NH3 gas volume ratio accounts for 5%) heat treatment (heat treated step is: be warming up to 400 ℃ with 1 hour from room temperature, at 400 ℃ of constant temperature after 8 hours, with dropping to room temperature in two hours), 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, drop to room temperature with 3 hours, atmosphere is the ammonia nitrogen gaseous mixture, and NH3 gas volume ratio accounts for 5%).Preparation-obtained meso-hole structure doping phosphoric acid lithium iron material 4 primary particle average grain diameters are 100nm, and the second particle average grain diameter is 4um, and mesoporous average pore size is 150nm.
The meso-hole structure doped iron lithium phosphate material in embodiment 5, oxygen room
The LiFePO4 matrix material LiFePO3.7N0.3 of oxygen-containing vacancy can prepare by following steps.At first, take by weighing the H3PO4 of the LiAc2H2O of 1.275g, the Fe of 3.114g (Ac) 24H2O and 1.225g respectively, add and fill in the beaker of 150ml ethylene glycol, use magnetic stirrer extremely evenly to disperse in 0.5 hour, add NH4H2O and regulate the pH value to 7-8, the continuation magnetic agitation was heat-treated this colloidal sol (heat treatment step is: with 100 ℃ of heating of colloidal sol 5 hours, be warming up to 120 ℃ then until becoming xerogel) to forming colloidal sol in 5 hours in high-purity N 2 gas.With this mixture under high-purity Ar gas/hydrogen mixed gas (H2 gas volume ratio accounts for 8%) protection heat treatment (heat treated step is: be warming up to 400 ℃ with 1 hour from room temperature; at 400 ℃ of constant temperature after 4 hours; with dropping to room temperature in two hours); with mixture once more sintering (sintering step is: be warming up to 600 ℃ with 2 hours from room temperature; at 600 ℃ of constant temperature after 8 hours, with dropping to room temperature in 3 hours.Obtain nitrogenous doped iron phosphate lithium basis material LiFePO3.7N0.3 dusty material, its primary particle average grain diameter is 80nm, and the second particle average grain diameter is 2um, and mesoporous average pore size is 50nm.
Embodiment 6～47
The chemical composition of meso-hole structure material 6～47 is referring to subordinate list 1.Similar to Example 1, different is, has prepared the Li doped MPO4 that contains different doped chemicals and ratio, basis material, and the LiMPO4 basis material that mixes of nitrogen, its expression formula can be written as LixAaMmBbPOzNn.Wherein, A is Na, Mg, and Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In, Ge, M are Fe, Co, Mn, Ni; B is Li, Na, and K, Ca, Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In, Ge; And M and B are not a kind of element simultaneously; X, a, m, b, z, n represents molar percentage, 0.9≤x≤1.8; 0≤a≤0.1; 0.5≤m≤1; 0≤b≤0.5; 3≤z≤4; 0≤n≤1.
Above-mentioned meso-hole structure olive material hot treatment method is similar to embodiment 3～5, different is preparation method's difference of presoma, the heat-treat condition difference, about the preparation of these materials, can be with reference to (Wang Deyu, Chen Liquan, Li Hong, yellow-study outstanding person, a kind of positive electrode and purposes that is used for serondary lithium battery, 200410031151.x; Li Hong, yellow-study outstanding person is used for the lithium iron phosphate positive material and uses thereof of the oxygen-containing vacancy of serondary lithium battery, 200410101618.3; Li Hong, yellow-study outstanding person, Wang Deyu, Chen Liquan, positive electrode of a kind of nitrogen phosphate that is used for serondary lithium battery and uses thereof, 200410037502.8).Because the reaction precursor substrate concentration, heat treatment temperature, heat treatment time there are differences, and these differences cause primary particle average grain diameter, second particle average grain diameter and the mesoporous average pore size of the mesoporous material that grows out there are differences.The feature of these mesoporous materials is listed in table 1.
Embodiment 48, meso-hole structure NASICON section bar material Li3V2 (PO4) 3
Meso-hole structure NASICON section bar material Li3V2 (PO4) 3 can prepare by following steps.At first, take by weighing the LiAcH2O of 1.275g respectively, 1.463gNH4VO3 and the H3PO4 of 1.225g, add and fill in the beaker of 800ml ethanol, use magnetic stirrer to forming colloidal sol, this colloidal sol is heat-treated in air (heat treatment step is: with colloidal sol 120 ℃ the heating 1 hour, be warming up to 140 ℃ then until becoming xerogel), xerogel is carried out sintering under air (sintering step is: be warming up to 700 ℃ with 3 hours from room temperature, at 700 ℃ of constant temperature after 12 hours, 5 hours cool to room temperature again).Resulting meso-hole structure NASICON section bar material Li3V2 (PO4) 3, the primary particle average grain diameter is 400nm, and the second particle average grain diameter is 8um, and mesoporous average pore size is 150nm.
This meso-hole structure NASICON section bar material Li3V2 (PO4) 3 mixed formation slurry (active material: acetylene black: PVDF=92: 5: 3) at normal temperatures and pressures with the n-formyl sarcolysine base pyrrolidone solution of acetylene black and 3% Kynoar (PVDF), evenly be coated on the aluminum substrates, then 100 ℃ of vacuumizes after 5 hours, the film of gained is compressed under 10MPa pressure, the about 100 μ m of the film thickness of gained are cut into the positive pole of the electrode slice of 1x1cm as simulated battery.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is dissolved in for 1mol LiPF6 in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery: at first charge to 5V with 30mA/g, the multiplying power current discharge is to 2.5V then, the capacity of being emitted reaches 120mAh/g with the Mass Calculation of meso-hole structure Li3V2 (PO4) 3, when discharging current increases to 1500mA/g, the discharge capacity of this material is 80mAh/g, this current density is equivalent to the charge-discharge magnification of 10C, and this result shows that meso-hole structure Li3V2 (PO4) 3 has high-multiplying power discharge characteristic preferably.
Embodiment 49, the coating mesoporous structure iron lithium phosphate of carbon material
The LiFePO4 that does not have carbon coated that embodiment 1 obtains can carry out carbon by the method for chemical vapour deposition (CVD) and coat.Be carbon source with acetylene, toluene etc. for example, do carrier gas with nitrogen, take by weighing 1.0gLiFePO4 and be put in the aluminium oxide magnetic boat, the magnetic boat is put in the boiler tube of tube furnace, begins to feed inert protective gas nitrogen, and regulating the stream of nitrogen gas amount is 80sccm.Service routine heats up and to be warming up to 700 ℃ with 1 hour from room temperature, begins to feed the nitrogen of carbonaceous sources composition again, at 700 ℃ of constant temperature after 2 hours, with dropping to room temperature in two hours.The mesoporous LiFePO4 material that obtains for the coating carbon-coating, wherein LiFePO4 primary particle average grain diameter is 80nm, the second particle average grain diameter is 5um, mesoporous average pore size is 90nm, the mass percent of carbon is 12% in the product, the mass percent of LiFePO4 is 88%, and the average thickness of carbon-coating is 20nm.
Embodiment 50, the coating mesoporous structure iron lithium phosphate of carbon material
The LiFePO4 that does not have carbon coated that embodiment 1 obtains can carry out carbon by the method for organic substance pyrolysis and coat.With organic substances such as sucrose, resins is carbon source; with ethanol etc. is solvent; take by weighing 0.3g sucrose and be dissolved in 20ml ethanol; add this sucrose ethanolic solution taking by weighing 1.0g LiFePO4; after the ethanol volatilization is treated in heating, move in the aluminium oxide magnetic boat, the magnetic boat is put in the boiler tube of tube furnace; begin to feed inert protective gas nitrogen, regulating the stream of nitrogen gas amount is 80sccm.Service routine heats up and to be warming up to 700 ℃ with 1 hour from room temperature, at 700 ℃ of constant temperature after 5 hours, with dropping to room temperature in two hours.The mesoporous LiFePO4 material that obtains for the coating carbon-coating, wherein LiFePO4 primary particle average grain diameter is 80nm, the second particle average grain diameter is 5um, mesoporous average pore size is 90nm, the mass percent of carbon is 8% in the product, the mass percent of LiFePO4 is 92%, and the average thickness of carbon-coating is 15nm.
Embodiment 51～55, the coating mesoporous structure olivine of carbon material
Be similar to embodiment 49, obtain the LiMPO4 that carbon-coating coats.The material difference of the LiMPO4 that different coated, its preparation method is identical with embodiment 1～5.Carbon coats the final content difference of back carbon in basis material, not being both because due to the carbon vapour deposition time of content.The final mass percent of carbon in the coating mesoporous material of carbon is no more than 20%, is not less than 1%.The principal character of the coating mesoporous structural material of resulting carbon is listed in table 2.
Embodiment 56～60, the coating mesoporous structure olivine of carbon material
Be similar to embodiment 50, obtain the LiMPO4 that carbon-coating coats.The material difference of the LiMPO4 that different coated, its preparation method is identical with embodiment 1～5.Carbon coats the final content difference of back carbon in basis material, not being both owing to be added with due to the part by weight difference of organic polymer of content.Organic amount is adding fashionable 0～30% weight ratio that generally is controlled at.The final mass percent of carbon in the coating mesoporous material of carbon is no more than 20%, is not less than 1%.The principal character of the coating mesoporous structural material of resulting carbon is listed in table 2.
The principal character of table 1 meso-hole structure olivine provided by the invention or NASICON type positive electrode
The principal character of the coating mesoporous structural material of table 2 carbon provided by the invention
Phosphate material having mesoporous structure provided by the invention can improve the high rate performance of existing phosphate material battery.The serondary lithium battery that contains this meso-hole structure material has the big remarkable advantage of power density.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and modification according to the present invention, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.
Claims (11)
1, a kind of olivine or sodium fast-ionic conductor type lithium transition metal phosphates material with meso-hole structure, it is characterized in that, this mesoporous material is the primary particle of the LiMPO4 of the pure phase phosphate LiMPO4 of 10nm～1um or doping by average grain diameter, form second particle through reuniting again, form mesoporous between the described primary particle with nanoscale mesopore orbit;
The chemical composition of the LiMPO4 of described doping is represented with following formula:
LixAaMmBbPOxNn
Wherein, in the formula of described pure phase phosphate LiMPO4 or LixAaMmBbPOxNn, A is Na, Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In or Ge;
M is Fe, Co, Mn, Ni or V;
B is Li, Na, K, Ca, Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In or Ge;
And M and B are not with a kind of element simultaneously;
X, a, m, b, z and n represent molar percentage, 0.9≤x≤1.8; 0≤a≤0.1; 0.5≤m≤1; 0≤b≤0.5; 3≤z≤4; 0≤n≤1.
2, olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material with meso-hole structure as claimed in claim 1, it is characterized in that: also be included in described second particle surface, or described mesoporous inwall deposition to coat a layer thickness be the carbon film of 2～100nm, the content of carbon accounts for 1～20wt% of mesoporous material weight.
3, olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material with meso-hole structure as claimed in claim 1, it is characterized in that: the geometric shape of described second particle is sphere or elliposoidal, average grain diameter is 100nm～50um.
4, olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material with meso-hole structure as claimed in claim 1, it is characterized in that: described mesoporous average pore size is 2～500nm, and described nanoscale mesopore orbit is to connect continuously or the partial continuous perforation.
5. one kind prepares the olivine with meso-hole structure or the method for sodium fast-ionic conductor type lithium transition metal phosphates material, it is characterized in that, may further comprise the steps:
1) preparation of colloidal sol: the preparation of the colloidal sol of pure phase phosphate LiMPO4 is with lithium salts, transition metal salt and phosphoric acid, be in molar ratio (1～1.1): 1: (1～1.05) adds in the solvent, stirred 0.5～1.5 hour, formation concentration is 0.01～2 mole homogeneous solution, adds NH4H2O again and regulate the pH value of this solution until continuing after 6～8 to stir till formation colloidal sol in this solution;
1 ') preparation of doped meso-porous structure phosphate LixAaMmBbPOzNn colloidal sol: be in above-mentioned steps 1) the colloidal sol preparation process in, add transition metal salt a kind of of the corresponding element of pressing the chemical dosage ratio among the chemical formula LixAaMmBbPOzNn;
Metal A is: Na, and Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In, Ge,
Metal M is Fe, Co, Mn, Ni or V;
Metal B is Li, Na, K, Ca, Mg, Ti, V, Cr, Cu, Mn, Co, Ni, Zn, Ga, In, Ge; And M and B are not with a kind of element simultaneously;
X, a, m, b, z, n represents molar percentage, 0.9≤x≤1.8; 0≤a≤0.1; 0.5≤m≤1; 0≤b≤0.5; 3≤z≤4; 0≤n≤1;
2) heat-treat the formation xerogel: described colloidal sol is heat-treated under air or inert atmosphere protection, and heat treatment temperature is between 60 ℃～200 ℃, and heating is until with the solvent evaporate to dryness, thereby obtains the predecessor of phosphate material having mesoporous structure, i.e. xerogel; Heating process is carried out under air, and when selected transition metal salt can oxidation take place under this heating-up temperature, then heating process was carried out under high-purity Ar or N2 gas shiled;
3) high temperature sintering: with step 2) xerogel that obtains carries out solid-phase sintering in air, and perhaps selected transition metal salt in high-purity Ar, carries out sintering in N2 or the Ar/H2 gaseous mixture when sintering;
Described sintering temperature is between 400 ℃～900 ℃, sintering time is 3～48 hours, natural cooling obtains the micron order olivine with meso-hole structure that is made of the nanoscale primary particle or the second particle of sodium fast-ionic conductor type lithium transition-metal material, the spherical in shape or elliposoidal of this particle then.
6, preparation as claimed in claim 5 has the method for the olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material of meso-hole structure, it is characterized in that: also be included in and carry out carbon again on the second particle of micron order olivine with meso-hole structure that step 3) obtains or sodium fast-ionic conductor type lithium transition-metal material and coat, the preparation technology of described coated with carbon comprises chemical vapour deposition (CVD), solid-phase sintering or uses liquid phase to coat the method for carbon-coating.
7, preparation as claimed in claim 5 has the method for the olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material of meso-hole structure, and it is characterized in that: described lithium salts comprises lithium acetate, lithium citrate, lithium nitrate or lithium oxalate.
8, preparation as claimed in claim 5 has the method for the olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material of meso-hole structure, and it is characterized in that: described transition metal salt comprises: acetate, citrate, nitrate or oxalates.
9, preparation as claimed in claim 5 has the method for the olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material of meso-hole structure, it is characterized in that: the solvent that uses in the described step 1) comprises: ethylene glycol, ethanol, methyl alcohol, glycerol, isopropyl alcohol or polyethylene glycol, or ethylene glycol, glycerol, two or more mixing in isopropyl alcohol or the polyethylene glycol.
10, preparation as claimed in claim 5 has the method for the olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material of meso-hole structure, it is characterized in that: described step 1 ') described in transition metal salt comprise: acetate, citrate, nitrate or oxalates.
11, preparation as claimed in claim 5 has the method for the olivine or the sodium fast-ionic conductor type lithium transition metal phosphates material of meso-hole structure, and it is characterized in that: described inert gas is Ar, N2 or Ar/H2 gaseous mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810102098A CN101540398A (en) | 2008-03-17 | 2008-03-17 | Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810102098A CN101540398A (en) | 2008-03-17 | 2008-03-17 | Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101540398A true CN101540398A (en) | 2009-09-23 |
Family
ID=41123467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810102098A Pending CN101540398A (en) | 2008-03-17 | 2008-03-17 | Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101540398A (en) |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101867042A (en) * | 2010-06-28 | 2010-10-20 | 彩虹集团公司 | Preparation method of nanometer level metallic lithium phosphate salt LiMPO4 |
| CN101964411A (en) * | 2010-08-25 | 2011-02-02 | 宁波金和新材料股份有限公司 | LiFePO4 composite type positive pole material and preparation method thereof |
| CN101969110A (en) * | 2010-08-31 | 2011-02-09 | 天津巴莫科技股份有限公司 | Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method |
| EP2360117A2 (en) * | 2008-10-22 | 2011-08-24 | LG Chem, Ltd. | Lithium iron phosphate having an olivine structure, and preparation method thereof |
| EP2424013A1 (en) * | 2010-08-31 | 2012-02-29 | Samsung SDI Co., Ltd. | Cathode active material, method of preparing the same, and cathode and lithium battery including the cathode active material |
| CN102456881A (en) * | 2010-10-18 | 2012-05-16 | 中国科学院物理研究所 | Olivine type phosphate cathode material and preparation method thereof as well as positive electrode and battery both containing olivine type phosphate cathode material |
| CN102522550A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Tantalum-doped carbon-coated lithium iron phosphate and preparation method for same |
| CN102522552A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Preparation method for doping lithium iron phosphate at lithium position |
| CN102694201A (en) * | 2012-06-04 | 2012-09-26 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN102694164A (en) * | 2012-06-08 | 2012-09-26 | 南开大学 | Lithium oxide-rich cathode material with nitrogen or carbon-doped surface and preparation method for cathode material |
| EP2538473A1 (en) * | 2011-06-24 | 2012-12-26 | Samsung SDI Co., Ltd. | Composite cathode active material, cathode and lithium battery including the composite cathode active material, and method of preparing the composite cathode active material |
| CN103098273A (en) * | 2010-09-09 | 2013-05-08 | Sk新技术株式会社 | Positive electrode active material for a lithium secondary battery, method for producing same, and lithium secondary battery comprising same |
| CN103137970A (en) * | 2013-03-04 | 2013-06-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous manganese phosphate lithium-carbon composite material and preparation method |
| CN103270628A (en) * | 2010-12-17 | 2013-08-28 | 住友大阪水泥股份有限公司 | Electrode material and method for producing same |
| CN103503207A (en) * | 2011-04-28 | 2014-01-08 | 昭和电工株式会社 | Method for producing positive electrode active material for lithium secondary battery |
| CN103811761A (en) * | 2012-11-07 | 2014-05-21 | 佛山市顺德区精锐电池科技有限公司 | Quick-charging lithium battery |
| CN104037407A (en) * | 2014-05-22 | 2014-09-10 | 北大先行科技产业有限公司 | Lithium cobalt oxide compound material coated with lithium super-Ion conductor and preparation method thereof |
| CN104192819A (en) * | 2014-07-14 | 2014-12-10 | 上海应用技术学院 | Clubbed phosphor-doped mesoporous carbon as well as preparation method and application thereof |
| CN105659413A (en) * | 2013-10-31 | 2016-06-08 | 普莱昂股份有限公司 | Wet method for the production of thin films |
| EP2654108A4 (en) * | 2010-12-17 | 2016-08-10 | Eliiy Power Co Ltd | Positive electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery and battery module |
| CN108511712A (en) * | 2018-03-23 | 2018-09-07 | 溧阳天目先导电池材料科技有限公司 | Lithium-ion electric subconductivity agent material, preparation method, lithium battery pole slice and lithium battery |
| CN109792048A (en) * | 2016-09-30 | 2019-05-21 | 松下知识产权经营株式会社 | Positive electrode for nonaqueous electrolyte secondary battery |
| CN110034280A (en) * | 2018-03-23 | 2019-07-19 | 溧阳天目先导电池材料科技有限公司 | A kind of In-situ reaction lithium cell cathode material and its preparation method and application |
| CN110212167A (en) * | 2018-02-28 | 2019-09-06 | 中信国安盟固利动力科技有限公司 | A kind of positive additive and preparation method thereof by metal oxide cladding |
| CN110444747A (en) * | 2019-07-29 | 2019-11-12 | 盐城工学院 | A kind of high performance carbon cladding metal phosphate nano material and its preparation method and application |
| CN111162322A (en) * | 2020-03-26 | 2020-05-15 | 隆能科技(南通)有限公司 | Preparation method of low-temperature lithium ion battery |
| CN111276733A (en) * | 2020-04-21 | 2020-06-12 | 隆能科技(南通)有限公司 | Safe low-temperature lithium ion battery capable of being charged and discharged quickly and preparation method thereof |
| CN111370752A (en) * | 2020-04-08 | 2020-07-03 | 隆能科技(南通)有限公司 | Fast charging and safe low temperature lithium ion battery and method of manufacturing the same |
| JP7121165B1 (en) * | 2021-06-11 | 2022-08-17 | 住友化学株式会社 | Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery |
| WO2024071408A1 (en) * | 2022-09-30 | 2024-04-04 | 日本ケミコン株式会社 | Electrode material, power storage device, and method for producing electrode material |
-
2008
- 2008-03-17 CN CN200810102098A patent/CN101540398A/en active Pending
Cited By (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2360117A2 (en) * | 2008-10-22 | 2011-08-24 | LG Chem, Ltd. | Lithium iron phosphate having an olivine structure, and preparation method thereof |
| EP2360117B1 (en) * | 2008-10-22 | 2015-05-06 | LG Chem, Ltd. | Lithium iron phosphate having an olivine structure, and preparation method thereof |
| CN101867042A (en) * | 2010-06-28 | 2010-10-20 | 彩虹集团公司 | Preparation method of nanometer level metallic lithium phosphate salt LiMPO4 |
| CN101964411A (en) * | 2010-08-25 | 2011-02-02 | 宁波金和新材料股份有限公司 | LiFePO4 composite type positive pole material and preparation method thereof |
| CN101969110A (en) * | 2010-08-31 | 2011-02-09 | 天津巴莫科技股份有限公司 | Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method |
| EP2424013A1 (en) * | 2010-08-31 | 2012-02-29 | Samsung SDI Co., Ltd. | Cathode active material, method of preparing the same, and cathode and lithium battery including the cathode active material |
| CN102386395A (en) * | 2010-08-31 | 2012-03-21 | 三星Sdi株式会社 | Cathode active material, method of preparing the same, and cathode and lithium battery including the cathode active material |
| US8932481B2 (en) | 2010-08-31 | 2015-01-13 | Samsung Sdi Co., Ltd. | Cathode active material, method of preparing the same, and cathode and lithium battery including the cathode active material |
| CN102386395B (en) * | 2010-08-31 | 2015-08-26 | 三星Sdi株式会社 | Positive electrode active materials, its preparation method and comprise its positive pole and lithium battery |
| CN103098273A (en) * | 2010-09-09 | 2013-05-08 | Sk新技术株式会社 | Positive electrode active material for a lithium secondary battery, method for producing same, and lithium secondary battery comprising same |
| CN103098273B (en) * | 2010-09-09 | 2016-03-02 | Sk新技术株式会社 | The active positive electrode material of lithium secondary battery, its production method and comprise its lithium secondary battery |
| CN102456881B (en) * | 2010-10-18 | 2014-03-12 | 中国科学院物理研究所 | Olivine type phosphate cathode material and preparation method thereof as well as positive electrode and battery both containing olivine type phosphate cathode material |
| CN102456881A (en) * | 2010-10-18 | 2012-05-16 | 中国科学院物理研究所 | Olivine type phosphate cathode material and preparation method thereof as well as positive electrode and battery both containing olivine type phosphate cathode material |
| CN103270628B (en) * | 2010-12-17 | 2016-06-29 | 住友大阪水泥股份有限公司 | Electrode material and manufacture method thereof |
| EP2654108A4 (en) * | 2010-12-17 | 2016-08-10 | Eliiy Power Co Ltd | Positive electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery and battery module |
| CN103270628A (en) * | 2010-12-17 | 2013-08-28 | 住友大阪水泥股份有限公司 | Electrode material and method for producing same |
| CN103503207B (en) * | 2011-04-28 | 2016-01-20 | 昭和电工株式会社 | The manufacture method of positive active material for lithium secondary battery |
| US9745194B2 (en) | 2011-04-28 | 2017-08-29 | Showa Denko K.K. | Method of producing cathode active material for lithium secondary battery |
| JP6055761B2 (en) * | 2011-04-28 | 2016-12-27 | 昭和電工株式会社 | Method for producing positive electrode active material for lithium secondary battery |
| CN103503207A (en) * | 2011-04-28 | 2014-01-08 | 昭和电工株式会社 | Method for producing positive electrode active material for lithium secondary battery |
| EP2538473A1 (en) * | 2011-06-24 | 2012-12-26 | Samsung SDI Co., Ltd. | Composite cathode active material, cathode and lithium battery including the composite cathode active material, and method of preparing the composite cathode active material |
| US9391316B2 (en) | 2011-06-24 | 2016-07-12 | Samsung Sdi Co., Ltd. | Composite cathode active material, cathode and lithium battery including the composite cathode active material, and method of preparing the composite cathode active material |
| CN102522550A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Tantalum-doped carbon-coated lithium iron phosphate and preparation method for same |
| CN102522552A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Preparation method for doping lithium iron phosphate at lithium position |
| CN102694201A (en) * | 2012-06-04 | 2012-09-26 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN102694164A (en) * | 2012-06-08 | 2012-09-26 | 南开大学 | Lithium oxide-rich cathode material with nitrogen or carbon-doped surface and preparation method for cathode material |
| CN103811761A (en) * | 2012-11-07 | 2014-05-21 | 佛山市顺德区精锐电池科技有限公司 | Quick-charging lithium battery |
| CN103811761B (en) * | 2012-11-07 | 2016-07-06 | 佛山市顺德区精锐电池科技有限公司 | A kind of quick charge lithium battery |
| CN103137970B (en) * | 2013-03-04 | 2015-09-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous calcium phosphate ferromanganese lithium-carbon composite and preparation method thereof |
| CN103137970A (en) * | 2013-03-04 | 2013-06-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous manganese phosphate lithium-carbon composite material and preparation method |
| CN105684194A (en) * | 2013-10-31 | 2016-06-15 | 普莱昂股份有限公司 | Wet method for the production of thin films |
| CN105659413A (en) * | 2013-10-31 | 2016-06-08 | 普莱昂股份有限公司 | Wet method for the production of thin films |
| CN104037407B (en) * | 2014-05-22 | 2017-04-05 | 北大先行科技产业有限公司 | A kind of cobalt acid lithium composite of lithium superionic conductors cladding and preparation method thereof |
| CN104037407A (en) * | 2014-05-22 | 2014-09-10 | 北大先行科技产业有限公司 | Lithium cobalt oxide compound material coated with lithium super-Ion conductor and preparation method thereof |
| CN104192819B (en) * | 2014-07-14 | 2016-06-08 | 上海应用技术学院 | A kind of bar-shaped phosphorus doping mesoporous carbon and its preparation method and application |
| CN104192819A (en) * | 2014-07-14 | 2014-12-10 | 上海应用技术学院 | Clubbed phosphor-doped mesoporous carbon as well as preparation method and application thereof |
| CN109792048A (en) * | 2016-09-30 | 2019-05-21 | 松下知识产权经营株式会社 | Positive electrode for nonaqueous electrolyte secondary battery |
| CN110212167A (en) * | 2018-02-28 | 2019-09-06 | 中信国安盟固利动力科技有限公司 | A kind of positive additive and preparation method thereof by metal oxide cladding |
| CN108511712A (en) * | 2018-03-23 | 2018-09-07 | 溧阳天目先导电池材料科技有限公司 | Lithium-ion electric subconductivity agent material, preparation method, lithium battery pole slice and lithium battery |
| CN110034280A (en) * | 2018-03-23 | 2019-07-19 | 溧阳天目先导电池材料科技有限公司 | A kind of In-situ reaction lithium cell cathode material and its preparation method and application |
| CN110034280B (en) * | 2018-03-23 | 2020-07-14 | 溧阳天目先导电池材料科技有限公司 | In-situ composite lithium battery negative electrode material and preparation method and application thereof |
| CN108511712B (en) * | 2018-03-23 | 2020-09-01 | 溧阳天目先导电池材料科技有限公司 | Lithium ion conductive agent material, preparation method, lithium battery pole piece and lithium battery |
| CN110444747A (en) * | 2019-07-29 | 2019-11-12 | 盐城工学院 | A kind of high performance carbon cladding metal phosphate nano material and its preparation method and application |
| CN111162322A (en) * | 2020-03-26 | 2020-05-15 | 隆能科技(南通)有限公司 | Preparation method of low-temperature lithium ion battery |
| CN111370752A (en) * | 2020-04-08 | 2020-07-03 | 隆能科技(南通)有限公司 | Fast charging and safe low temperature lithium ion battery and method of manufacturing the same |
| CN111276733A (en) * | 2020-04-21 | 2020-06-12 | 隆能科技(南通)有限公司 | Safe low-temperature lithium ion battery capable of being charged and discharged quickly and preparation method thereof |
| JP7121165B1 (en) * | 2021-06-11 | 2022-08-17 | 住友化学株式会社 | Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery |
| WO2024071408A1 (en) * | 2022-09-30 | 2024-04-04 | 日本ケミコン株式会社 | Electrode material, power storage device, and method for producing electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101540398A (en) | Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof | |
| US20230322557A1 (en) | Method for preparing lithium manganese iron phosphate, cathode material, and lithium-ion battery | |
| CN106876705B (en) | Preparation method of in-situ synthesized carbon/carbon nanotube coated lithium iron phosphate composite material | |
| Pan et al. | Hydrothermal synthesis of well-dispersed LiMnPO4 plates for lithium ion batteries cathode | |
| CN109244391B (en) | Nitrogen-doped carbon-coated lithium manganese iron phosphate material and preparation method thereof | |
| CN102456881B (en) | Olivine type phosphate cathode material and preparation method thereof as well as positive electrode and battery both containing olivine type phosphate cathode material | |
| CN101826617B (en) | Preparation method of lithium iron phosphate | |
| CN101420034A (en) | Carbon coated granularity controllable spherical lithium ferric phosphate composite positive pole material and preparation method thereof | |
| CN109103433B (en) | Nitrogen-doped carbon-coated lithium iron phosphate composite material and preparation method thereof | |
| CN105226273B (en) | A kind of iron manganese phosphate for lithium and preparation method and application | |
| CN101237043A (en) | Method for making ferrous lithium phosphate/carbon compound material of high active disorderly ferric phosphate | |
| CN103560246B (en) | A kind of preparation method of lithium ion battery anode material lithium iron phosphate | |
| CN102110814B (en) | Preparation method of lithium iron phosphate and battery anode | |
| CN101339991B (en) | Composite coated modified high vibrancy solid lithium ionic battery positive electrode, preparation and application thereof | |
| CN109037659A (en) | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material | |
| Li et al. | Optimized synthesis of LiFePO4 composites via rheological phase assisted method from FePO4 with acetic acid as dispersant | |
| CN102479945B (en) | The preparation method of spherical lithium iron phosphate anode material | |
| CN114665058A (en) | Preparation method of lithium ion battery anode material lithium iron manganese phosphate | |
| EP2619137A1 (en) | A two-step synthesis method for the preparation of composites of insertion active compounds for lithium-ion batteries | |
| CN105609769A (en) | Preparation method for multi-level structured molybdenum disulfide microsphere negative electrode material of lithium battery | |
| CN107910538A (en) | Graphene/carbon coats lithium manganese phosphate vanadium phosphate cathode material and preparation method | |
| CN113725418A (en) | Rare earth oxide coated and modified ternary cathode material for lithium ion battery and preparation method thereof | |
| Zhang et al. | Preparation of neodymium‐doped LiMnPO4/C cathode by sol‐gel method with excellent electrochemical performance for lithium‐ion batteries | |
| CN102034958A (en) | Mesoporous phosphate anode material with olivine structure and preparation method and use thereof | |
| Wu et al. | Preparation and characterization of spinel Li 4 Ti 5 O 12 nanoparticles anode materials for lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20090923 |