CN102064317B - LiFe1-xMxPO4 compound containing carbon element and preparation method thereof - Google Patents
LiFe1-xMxPO4 compound containing carbon element and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a new compound LiFe1-xMxPO4/C, wherein M is Mn, Co, Ni, Al or V, and x is no less than 0 and no more than 1. The invention also discloses a lithium ion battery positive electrode material containing the new compound and a preparation method of the compound. The LiFe1-xMxPO4/C compound disclosed by the invention has excellent electrochemistry performance, is prepared by adopting a low thermosetting phase reaction method, the process is simple,the synthesis temperature is lower, the price of the used material is low, and the compound LiFe1-xMxPO4/C is convenient for large-scale production.
Description
Technical field
The present invention relates to lithium ion battery field, particularly relate to a kind of LiFe
1-xm
xpO
4/ C compound, its preparation method and in lithium rechargeable battery as the application of positive electrode.
Background technology
Lithium rechargeable battery have have extended cycle life, the plurality of advantages such as the large and memory-less effect of discharging voltage balance, specific capacity, make it in the extensive use of the numerous areas such as mobile phone, notebook computer and portable electronic device, more and more be subject to the public's concern and favor.Along with the development of mixed power electric car and secondary cell electric automobile, the capacity of rechargeable battery and quality were had higher requirement in recent years.
The LiFePO with olivine structural
4be the existing compound of occurring in nature, because of its multiplying power and security performance with stable structure, excellence, be expected to become anode material for lithium-ion batteries of new generation.
1997, the people such as Goodenough in patent WO9740541, reported the LiFePO preparing in inert atmosphere first
4the chemical property of compound, thus people's common concern caused.Prepare at present LiFePO
4the method of compound is mainly high temperature solid-state method (dry method) and some solwution methods (wet method), as sol-gel process, and coprecipitation, hydro thermal method etc.The major defect of these methods is exactly that operation is loaded down with trivial details, and particularly conventional solid-state method has high-temperature, and the shortcoming of long-time and high energy consumption, has so just brought very large drawback to industrial production.
Rare earth method is used as metal-organic preparation (Braga, D., Chemical Review, 92 (1992) 633-665 the earliest as a kind of softening method; Zhu, M., Li, Y.R., Luo, J.and Zhou X.G, Chinese Science Bulletin, 48 (2003) 2041-2043; CN1068811A).The method is progressively applied to the preparation process of inorganic material at present.Wherein CN03131933.5 discloses a kind of method that low fever solid phase reaction is prepared lithium manganese oxide; CN200510011676.1 discloses a kind of method that adopts low fever solid phase reaction to prepare laminar oxide material of lithium, cobalt, nickel and manganese; CN200510086505.5 discloses the method for utilizing low fever solid phase reaction to prepare Li, Ni, Mn oxide material.But for LiFePO
4class material, at present not yet relevant for the bibliographical information that adopts low fever solid phase reaction method to be prepared.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of LiFe of new carbon elements is provided
1-xm
xpO
4compound (LiFe
1-xm
xpO
4/ C) and the lithium ion secondary battery anode material that contains this compound.
Still a further object of the present invention is to provide above-mentioned LiFe
1-xm
xpO
4simple, the preparation method of being convenient to large-scale production of/C compound.
For achieving the above object, the invention provides a kind of new compound: the LiFe of carbon elements
1-xm
xpO
4(LiFe
1-xm
xpO
4/ C), M is Mn, Co, Ni, Al or V, 0≤x≤1.
C connects and/or carbon doping and LiFe by weak interaction force, chemical bond key
1-xm
xpO
4be connected, and preferred 0 < x < 0.2.
The present invention also provides the anode material for lithium-ion batteries that contains above-claimed cpd.
The present invention further provides the above-mentioned LiFe of preparation
1-xm
xpO
4the method of/C compound, described method is low fever solid phase reaction method, described method comprises:
The preparation of predecessor:
A, by the oxide of organic acid molysite or ferrous salt, Li source compound, oxalic acid, phosphate and M element or acetate according to Li: Fe: H
2c
2o
4: M: PO
4=a: 1-x: 1: x: 1 ratio also adds organic substance to be mixed together evenly, wherein 1 < a < 1.1;
B, under the temperature conditions of 60 ℃～120 ℃, carry out low fever solid phase reaction 3～6h and obtain predecessor;
The preparation of compound:
C, under 550 ℃～800 ℃ and inert atmosphere, sintering obtains end-product for 5～14 hours.
In step a:
Described organic acid molysite or ferrous salt are preferably molysite or the ferrous salt of citric acid or oxalic acid;
Described Li source compound is preferably carbonate or the hydroxide of Li;
Described phosphate is preferably ammonium dihydrogen phosphate, ammonium hydrogen phosphate or ammonium phosphate;
Described organic substance comprises at least one in polyethylene, dextrin, sucrose, glucose, starch and phenolic resins;
Organic addition is the theoretical LiFe of generation
1-xm
xpO
4weight 8%～35%.
In the preferred embodiment of the present invention, described step b further comprises, before low fever solid phase reaction, adds appropriate amount of deionized water, and dry after low fever solid phase reaction at step a in the product mixing.
In step c, described inert atmosphere is preferably nitrogen or argon gas atmosphere.
Owing to having adopted above technical scheme, the beneficial effect that the present invention possesses is:
LiFe of the present invention
1-xm
xpO
4/ C compound has excellent chemical property, has higher electronic conductivity, when it is applied as lithium ion secondary battery anode material, has higher specific capacity and cycle efficieny.
The present invention adopts low fever solid phase reaction legal system for LiFe
1-xm
xpO
4/ C compound, with respect to conventional solid-state method, the method, without carrying out long-time grinding in early stage, has lower calcination temperature and shorter reaction time simultaneously in the preparation process of material.The method process is simple, and synthesis temperature is lower, and material therefor is cheap, is convenient to large-scale production.
Accompanying drawing explanation
Fig. 1 is LiFePO prepared in embodiment 1
4the XRD spectra of/C compound;
Fig. 2 is LiFePO prepared in embodiment 2
4the XRD spectra of/C compound;
Fig. 3 is LiFe prepared in embodiment 3
0.99ni
0.01pO
4the XRD spectra of/C compound;
Fig. 4 is LiFe prepared in embodiment 4
0.97ni
0.03pO
4the XRD spectra of/C compound;
Fig. 5 is LiFe prepared in embodiment 5
0.89co
0.11pO
4the XRD spectra of/C compound;
Fig. 6 is LiFe prepared in embodiment 6
0.95al
.0.05pO
4the XRD spectra of/C compound;
Fig. 7 is LiFe prepared in embodiment 7
0.85v
.0.15pO
4the XRD spectra of/C compound;
Fig. 8 is LiFePO prepared in embodiment 1 and 2
4the first charge-discharge curve of/C compound;
Fig. 9 is the LiFe preparing respectively in embodiment 3,4,5
0.09ni
0.01pO
4/ C compound, LiFe
0.97ni
0.03pO
4/ C compound and LiFe
0.89co
0.11pO
4the first charge-discharge curve of/C compound;
Figure 10 is the prepared LiFe of embodiment 6
0.95al
.0.05pO
4the first charge-discharge curve of/C compound;
Figure 11 is the prepared LiFe of embodiment 7
0.85v
.0.15pO
4the first charge-discharge curve of/C compound.
Embodiment
At LiFePO
4in structure, Fe and Li form respectively FeO
6and LiO
6octahedron, P forms PO
4tetrahedron.Adjacent FeO
6the octahedra FeO that has formed a Z-shaped structure by sharing an O atom on bc face
6layer.In charge and discharge process, Li+ ion can take off in reversible embedding, corresponding to Fe
3+/ Fe
2+mutual conversion, platform voltage is 3.50V, and platform is more steady.Because the bond energy of P-O key is very large, PO
4for inertia, thereby can to play support structure effect highly stable in removal lithium embedded process for tetrahedron.Meanwhile, also just because of adjacent FeO
6octahedron connects by common summit, has hindered to a certain extent Li
+the free diffusing of ion, finally caused lower electronic conductivity (Thackeray, M., Lithium-ion batteries:An unexpected conductor.Nat Mater2002,1, (2), 81-82.), in order fundamentally to solve the lower electronic conductivity of material, we have synthesized LiFe
1-xm
xpO
4/ C material, in this material, M is divalence or Tricationic, and radius is less than Fe
2+, the MO being formed by it in this compound
6thereby octahedron will occupy relatively little space and be conducive to Li
+the free diffusing of ion, therefore can fundamentally improve LiFePO
4the electronic conductivity of material, improves the telephony performance of material.
Noval chemical compound LiFe of the present invention
1-xm
xpO
4in/C, M is Mn, Co, Ni, Al or V, 0≤x≤1, preferably 0 < x < 0.2.C atom and LiFe in this compound
1-xm
xpO
4between compound, mainly by weak interaction force and chemical bond key, connect, also can have the carbon doping of a little simultaneously, so just make LiFe
1-xm
xpO
4/ C compound has relatively traditional LiFePO
4the conductivity that compound is more excellent, thus make material be more suitable for lithium ion conventional batteries and electrokinetic cell field.
Noval chemical compound LiFe of the present invention
1-xm
xpO
4/ C possesses excellent chemical property, can be used as the positive electrode of lithium ion battery, and has higher specific capacity and cycle efficieny.
Noval chemical compound LiFe of the present invention
1-xm
xpO
4the preparation method of/C is to adopt the low fever solid phase reaction that is different from conventional high-temperature solid phase method.With respect to conventional solid-state method, method of the present invention, without carrying out long-time grinding in early stage, has lower calcination temperature and shorter reaction time simultaneously in the preparation process of material.The method process is simple, and synthesis temperature is lower, and material therefor is cheap, is convenient to large-scale production.
Preparation method of the present invention mainly comprises and prepares predecessor and prepare compound of the present invention by predecessor.
In the preparation process of predecessor, comprise the oxide of organic acid molysite or ferrous salt, Li source compound, oxalic acid, phosphate and M element (M is Mn, Co, Ni, Al or V) or acetate according to Li: Fe: H
2c
2o
4: M: PO
4=a: 1-x: 1: x: 1 ratio also adds the organic substance of proper proportion to be mixed together evenly, wherein must guarantee that Li element is excessive, 1 < a < 1.1, little on result impact when in course of reaction, Li element consumption changes within the scope of this.In preparation process, often select a=1.05; Then under the temperature conditions of 60 ℃～120 ℃, carry out low fever solid phase reaction 3～6h and obtain predecessor.
In the preparation process of predecessor, organic acid molysite or ferrous salt are preferably molysite or the ferrous salt of citric acid or oxalic acid, more preferably use ironic citrate (C
6h
5o
7fe5H
2o); Li source compound is preferably carbonate or the hydroxide of Li, more preferably uses LiOH; Phosphate is preferably ammonium dihydrogen phosphate, ammonium hydrogen phosphate or ammonium phosphate, more preferably uses ammonium dihydrogen phosphate; Organic addition is the theoretical LiFe of generation
1-xm
xpO
48%～35% of weight, and conventionally use simple organic, only need meet the simple organic that can decomposite organic carbon in inert environments and all be applicable to the present invention, such as can select in polyethylene, dextrin, sucrose, glucose, starch and phenolic resins at least one.Carry out low fever solid phase reaction under the temperature conditions of 60 ℃～120 ℃ before, preferably in mixture, add appropriate amount of deionized water.The object that adds appropriate deionized water is to provide a comparatively moist reaction environment to system, thereby is conducive to the preparation of material." in right amount " specifically finger can observe solid particles surface and have a little moist, the accurate consumption of deionized water is not particularly limited on this basis.After adding deionized water to carry out low fever solid phase reaction, further oven dry obtains the predecessor of the compounds of this invention.
The predecessor preparing sintering under 550 ℃～800 ℃ and inert atmosphere can be obtained to end product LiFe in 5～14 hours
1-xm
xpO
4/ C compound.Wherein, inert atmosphere is preferably nitrogen or argon gas atmosphere.
Below by specific embodiment, by reference to the accompanying drawings the present invention is described in further detail.
Embodiment 1
With Fe: Li: H
2c
2o
4: PO
4=1: the ratio of 1.05: 1: 1 takes respectively ironic citrate, LiOHH
2o, H
2c
2o
4and NH
4h
2pO
4after mixing, then to add the sucrose of proper proportion, the consumption of sucrose be the theoretical LiFePO of generation
4quality 10%.Then in the product mixing to these, add appropriate deionized water and make solid particles surface have a little humidity, in 100 ℃ of reaction 4h post-dryings, obtain predecessor, by the predecessor preparing 650 ℃ under argon gas atmosphere sintering within 8 hours, can obtain end product LiFePO
4/ C compound.
Embodiment 2
With Fe: Li: H
2c
2o
4: PO
4=1: the ratio of 1.05: 1: 1 takes respectively ironic citrate, LiOHH
2o, H
2c
2o
4and NH
4h
2pO
4after mixing, then to add the glucose of proper proportion, the consumption of glucose be the theoretical LiFePO of generation
4quality 10%.Then in the product mixing to these, add appropriate deionized water, in 60 ℃ reaction 6 hours post-dryings obtain predecessor, by the predecessor preparing 750 ℃ under nitrogen atmosphere sintering within 6 hours, can obtain end product LiFePO
4/ C compound.
Embodiment 3
With Fe: Li: H
2c
2o
4: Ni: PO
4=0.99: 1.05: 1: 0.01: 1 ratio takes respectively ironic citrate, LiOHH
2o, H
2c
2o
4, nickel acetate and NH
4h
2pO
4after mixing, then to add the sucrose of proper proportion, the consumption of sucrose be the theoretical LiFePO of generation
4quality 30%.Then in the product mixing to these, add appropriate deionized water, in 120 ℃ of reaction 3h post-dryings, obtain predecessor, by the predecessor preparing 550 ℃ under argon gas atmosphere sintering within 12 hours, can obtain end product LiFe
0.99ni
0.01pO
4/ C compound.
Embodiment 4
With Fe: Li: H
2c
2o
4: Ni: PO
4=0.97: 1.05: 1: 0.03: 1 ratio takes respectively ironic citrate, LiOHH
2o, H
2c
2o
4, nickel protoxide and NH
4h
2pO
4after mixing, then to add the glucose of proper proportion, the consumption of glucose be the theoretical LiFePO of generation
4quality 20%.Then in the product mixing to these, add appropriate deionized water, in 80 ℃ of reaction 5h post-dryings, obtain predecessor, the predecessor preparing can be obtained to end product LiFe in 8 hours at 650 ℃ of sintering
0.97ni
0.03pO
4/ C compound.
Embodiment 5
With Fe: Li: H
2c
2o
4: Co: PO
4=0.89: 1.05: 1: 0.11: 1 ratio takes respectively ironic citrate, LiOHH
2o, H
2c
2o
4, cobalt acetate and NH
4h
2pO
4after mixing, then to add the glucose of proper proportion, the consumption of glucose be the theoretical LiFePO of generation
4quality 20%.Then in the product mixing to these, add appropriate deionized water, in 80 ℃ of reaction 5h post-dryings, obtain predecessor, the predecessor preparing can be obtained to end product LiFe in 8 hours at 650 ℃ of sintering
0.89co
0.11pO
4/ C compound.
Embodiment 6
With Fe: Li: H
2c
2o
4: Al: PO
4=0.95: 1.05: 1: 0.05: 1 ratio takes respectively ironic citrate, LiOHH
2o, H
2c
2o
4, Al
2o
3and NH
4h
2pO
4after mixing, then to add the glucose of proper proportion, the consumption of glucose be the theoretical LiFePO of generation
4quality 20%.Then in the product mixing to these, add appropriate deionized water, in 80 ℃ of reaction 5h post-dryings, obtain predecessor, the predecessor preparing can be obtained to end product LiFe in 8 hours at 650 ℃ of sintering
0.95al
0.05pO
4/ C compound.
Embodiment 7
With Fe: Li: H
2c
2o
4: V: PO
4=0.85: 1.05: 1: 0.15: 1 ratio takes respectively ironic citrate, LiOHH
2o, H
2c
2o
4, vanadic oxide and NH
4h
2pO
4after mixing, then to add the glucose of proper proportion, the consumption of glucose be the theoretical LiFePO of generation
4quality 20%.Then in the product mixing to these, add appropriate deionized water, in 80 ℃ of reaction 5h post-dryings, obtain predecessor, the predecessor preparing can be obtained to end product LiFe in 8 hours at 650 ℃ of sintering
0.85v
0.15pO
4/ C compound.
Experimental example
Embodiment 1,2,3,4,5,6,7 is gained LiFe separately
1-xm
xpO
4the XRD spectral line of/C compound is respectively as shown in Fig. 1-Fig. 7.X-ray diffraction result shows the LiFe that adopts the method to prepare
1-xm
xpO
4/ C compound has very high purity, there is no the appearance of other impurity peaks, therefore can be used as lithium ion secondary battery anode material.
By the X-ray diffraction result of these materials by powder crystal software for calculation---Winplot calculates the cell parameter can obtain these materials, and cell parameter result, as shown in table-1, can be found out the LiFePO of preparation in embodiment 1 and 2 from result
4/ C has close cell parameter.Be respectively
with
and the LiFe preparing respectively by embodiment 3,4 and 5
0.99ni
0.01pO
4/ C, LiFe
0.97ni
0.03pO
4/ C and LiFe
0.89co
0.11pO
4the compound of/C has close cell parameter equally, is respectively 292.55,292.81 and
but than pure LiFePO
4the cell parameter of/C is little, and its main cause is the Ni due to less ionic radius
2+and Co
2+ion has occupied respectively Fe
2+should be at LiFePO
4position in structure cell, thus caused the unit cell volume of embodiment 3,4 and 5 to be less than the unit cell volume of embodiment 1 and 2 prepared compounds, Comparatively speaking, the LiFe that embodiment 6 and 7 prepares
0.95al
0.05pO
4/ C and LiFe
0.85v
0.15pO
4/ C material possesses less unit cell volume, and main cause is owing to having introduced respectively the less Tricationic Al of unit cell volume in this two classes composite material
3+and V
3+ion, and doping is relatively many.
The XRD structure cell result of calculation of-17 kinds of materials of table
Adopt the inventive method gained LiFe
1-xm
xpO
4the process that/C makes battery anode slurry is identical with battery anode slurry process in prior art.
By embodiment 1 gained LiFePO
4/ C and Super P, PVDF prepare anode sizing agent according to the ratio of 80: 15: 5 (mass ratio), after mixing with machine,massing, and slurry on small-sized tensile pulp machine, pole piece is used aluminium foil (thickness 16 μ m), and slurry surface density is 8-9mg/cm
2.Using metal Li as to electrode, and EC, EMC, DMC dissolve in the LiPF of 1mol/L at 1: 1: 1 according to volume ratio
6in make electrolyte, be full of argon shield and H
2o, O
2all be less than in the glove box of 1ppm and be assembled into half-cell.Half-cell is carried out to the experiment of constant current charge and discharge cycle with 0.1C, and charging is by voltage 3.8V, and electric discharge is by voltage 2.0V.
Embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and embodiment 7 gained LiFe
1-xm
xpO
4/ C compound also, respectively according to said process assembling half-cell, carries out the experiment of constant current charge and discharge cycle under above-mentioned same condition to half-cell.
First circle discharges and recharges result and first circle efficiency, can be found out as shown in the of-2 as shown
Table-2 embodiment 1-7 first circle specific discharge capacity and first circle efficiency
| Title | Specific discharge capacity mAh/g | First circle efficiency (%) |
| Embodiment 1 | 126.4 | 90.2 |
| Embodiment 2 | 129.0 | 91.6 |
| Embodiment 3 | 144.1 | 96.0 |
| Embodiment 4 | 140.3 | 94.9 |
| Embodiment 5 | 142.3 | 95.3 |
| Embodiment 6 | 152.3 | 97.1 |
| Embodiment 7 | 148.1 | 95.6 |
Charge and discharge cycle experimental result is as shown in Fig. 8-Figure 11.
In Fig. 8, the specific capacity of the cycle charging first 140.1mAh/g of embodiment 1 resulting materials, specific discharge capacity is 126.4mAh/g, first charge-discharge efficiency reaches 90.2%; The specific capacity of the cycle charging first 140.9mAh/g of embodiment 2 resulting materials, specific discharge capacity is 129.0mAh/g, first charge-discharge efficiency reaches 91.6%.Both are comparatively approaching.
In Fig. 9, the specific capacity of the cycle charging first 150.1mAh/g of embodiment 3 resulting materials, specific discharge capacity is 144.1mAh/g, first charge-discharge efficiency reaches 96.0%; The specific capacity of the cycle charging first 147.8mAh/g of embodiment 4 resulting materials, specific discharge capacity is 140.3mAh/g, first charge-discharge efficiency reaches 94.9%; The specific capacity of the cycle charging first 149.3mAh/g of embodiment 5 resulting materials, specific discharge capacity is 142.3mAh/g, first charge-discharge efficiency reaches 95.3%.
In Figure 10, the specific capacity of the cycle charging first 156.8mAh/g of embodiment 6 resulting materials, specific discharge capacity is 152.3mAh/g, first charge-discharge efficiency reaches 97.1%; The specific capacity of the cycle charging first 155.0mAh/g of Figure 11 embodiment 7 resulting materials, specific discharge capacity is 148.1mAh/g, first charge-discharge efficiency reaches 95.6%.
From Fig. 8, Fig. 9, Figure 10 and Figure 11, adopt the LiFe of the inventive method gained
1-xm
xpO
4/ C has excellent charge-discharge performance, meanwhile, by this method, prepares LiFe
0.99ni
0.01pO
4/ C, LiFe
0.97ni
0.03pO
4/ C, LiFe
0.89co
0.11pO
4/ C, LiFe
0.95al
0.05pO
4/ C and LiFe
0.85v
0.15pO
4/ C compound is than unadulterated LiFePO
4/ C compound has more excellent charge-discharge performance, and its main cause may be due to LiFe
0.09ni
0.01pO
4/ C, LiFe
0.97ni
0.03pO
4/ C, LiFe
0.89co
0.11pO
4/ C, LiFe
0.95al
0.05pO
4/ C and LiFe
0.85v
0.15pO
4in/C compound, have compared with the Ni of small ion radius
2+, Co
2+, Al
3+and V
3+it is FeO originally that the introducing of ion has caused
6octahedral smaller volume, makes Li
+ion has the diffusion space more strengthening, thereby has excellent chemical property from having improved in essence the electronic conductivity of compound.
Above content is in conjunction with concrete execution mode further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (7)
1. the LiFe of carbon elements
1-xm
xpO
4the preparation method of compound, wherein, M is Mn, Co, Ni, Al or V, 0≤x≤1, described method is low fever solid phase reaction method, described method comprises:
The preparation of predecessor:
A, by the oxide of organic acid molysite or organic acid ferrous salt, Li source compound, oxalic acid, phosphate and M element or acetate according to Li:Fe:H
2c
2o
4: M:PO
4the ratio of=a:1-x:1:x:1 also adds organic substance to be mixed together evenly, wherein 1<a<1.1;
B, under the temperature conditions of 60 ℃～120 ℃, carry out low fever solid phase reaction 3～6h and obtain predecessor;
The preparation of compound:
C, predecessor sintering under 550 ℃～800 ℃ and inert atmosphere is obtained to end-product for 5～14 hours.
2. method according to claim 1, is characterized in that: in step a, described organic acid molysite or organic acid ferrous salt are the molysite of citric acid or oxalic acid, or the ferrous salt of citric acid or oxalic acid.
3. method according to claim 2, is characterized in that: in step a, and the carbonate that described Li source compound is Li or hydroxide.
4. method according to claim 3, is characterized in that: in step a, described phosphate is ammonium dihydrogen phosphate, ammonium hydrogen phosphate or ammonium phosphate.
5. method according to claim 4, is characterized in that: in step a, described organic substance comprises at least one in polyethylene, dextrin, sucrose, glucose, starch and phenolic resins.
6. method according to claim 5, is characterized in that: in step a, organic addition is the theoretical LiFe of generation
1-xm
xpO
4weight 8%～35%.
7. method according to claim 6, is characterized in that: described step b further comprises, before low fever solid phase reaction, adds water, and dry after low fever solid phase reaction at step a in the product mixing.
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|---|---|---|---|
| CN200910110197.3A CN102064317B (en) | 2009-11-13 | 2009-11-13 | LiFe1-xMxPO4 compound containing carbon element and preparation method thereof |
| HK11111279.6A HK1157067A1 (en) | 2009-11-13 | 2011-10-20 | Carbon element included compound life1-xmxpo4 and the preparation method thereof life1-xmxpo4 |
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| CN105261732B (en) * | 2015-09-02 | 2018-05-29 | 武汉理工力强能源有限公司 | A kind of three-dimensional porous electrode material of vanadium doping lithium iron phosphate/carbon and preparation method thereof |
| CN106486668B (en) * | 2016-10-14 | 2019-07-16 | 山东省科学院能源研究所 | A kind of iron manganese vanadium phosphate precursor, iron manganese vanadium phosphate lithium/carbon cathode material and preparation method |
| CN109980295A (en) * | 2019-03-26 | 2019-07-05 | 陈林龙 | The preparation process of new energy resource power battery |
| CN112349904A (en) * | 2020-09-27 | 2021-02-09 | 江苏合志新能源材料技术有限公司 | Lithium ion battery multi-phosphate anode material and preparation method thereof, anode and lithium ion battery |
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| TWI319920B (en) * | 2006-07-06 | 2010-01-21 | The preparation and application of the lifepo4/li3v2(po4)3 composite cathode materials for lithium ion batteries |
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| CN1461064A (en) * | 2003-06-19 | 2003-12-10 | 南京大学 | Method for preparing lithium manganese oxide by using low-heat solid phase reaction |
| CN1269242C (en) * | 2005-04-30 | 2006-08-09 | 北京科技大学 | Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat |
| CN1321881C (en) * | 2005-09-23 | 2007-06-20 | 北京科技大学 | Method for preparing Li, Ni, Mn oxide material by adopting low-heat solid phase reaction |
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| CN102064317A (en) | 2011-05-18 |
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