CN103117385A - Defective-structure LiFePO4 surface-modified lithium-enriched layer-layer cathode material and preparation method thereof - Google Patents
Defective-structure LiFePO4 surface-modified lithium-enriched layer-layer cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a defective-structure LiFePO4 surface-modified lithium-enriched layer-layer composite cathode material. According to the defective-structure LiFePO4 surface-modified lithium-enriched layer-layer composite cathode material, the stoichiometric equation of a surface-modified layer is LiFe1-2yP1-yO4-sigma, wherein sigma= 4-[(1-2y)*2+1+(1-y)*5]/2, and y is 0.01 to 0.06; the stoichiometric equation of the lithium-enriched layer-layer composite cathode material is xLi2MnO3.(1-x)LiMnO.5Ni0.5O2 (x is not smaller than 0 and not more than 0.5); and the amount of substances of the surface-modified layer is 1-10% that of the cathode material. The surface-modified cathode material has the advantages of high cycle capacity retentiveness and excellent power multiplying characteristic.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and manufacture field.
Background technology
Lithium ion battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the high absolute advantage of power density, have in global portable power source market and exceed 30,000,000,000 dollars of/year shares the occupation rate of market that surpasses other batteries far away, the chemical power source [Wu Yuping that there is future develop most, Wan Chunrong, Jiang Changyin, lithium rechargeable battery, Beijing: Chemical Industry Press, 2002.].Yet, since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time between 100-180mAh/g, the low bottleneck that promotes the lithium ion battery specific energy that become of positive electrode specific capacity.If want effectively to improve the energy density of lithium ion battery, must consider from voltage difference and two aspects of exploitation height ratio capacity electrode material of improving between positive and negative pole material.
The current commercial lithium ion battery positive electrode of practicality the most widely is LiCoO
2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and larger toxicity arranged.Therefore in recent years, the researcher of countries in the world is devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, up till now, the lithium ion cell positive filtered out reaches tens of kinds, but potential commercial applications prospect is really arranged or the positive electrode that appeared on market very few really.As lithium manganate having spinel structure LiMn
2o
4its cost is lower, than being easier to preparation, security performance is also relatively good, yet capacity is lower, and theoretical capacity is 148mAh/g, actual capacity is at 100-120mAh/g, and this material capacity circulation hold facility is not good, under high temperature, capacity attenuation is very fast, and the researcher is being perplexed in the John-Teller effect of Mn3+ and the dissolving in electrolyte for a long time.The LiNiO of layer structure
2and LiMnO
2although larger theoretical specific capacity is arranged, be respectively 275mAh/g and 285mAh/g, their preparations are very difficult, poor heat stability, cyclicity is very poor, and capacity attenuation is very fast.And business-like LiFePO4 LiFePO progressively at present
4cost is low, Heat stability is good, environmental friendliness, but its theoretical capacity approximately only has 170mAh/g, and actual capacity is in the 140mAh/g left and right.
In recent years, the researcher gradually by high lithium than on positive electrode, particularly the high lithium of manganese base manganese-nickel binary and manganese base manganese-nickel-cobalt ternary solid solution system compares positive electrode, these materials have very high Capacity Ratio, high stability and relative cheap cost and are subject to people's concern [Young-Sik Hong, Yong Joon Park, et al., Solid State Ionics, 2005,176:1035～1042].Rich lithium material can be regarded Li as
2mnO
3and LiM ' O
2(M '=Mn, Co, Ni, Mn
0.5ni
0.5deng) continuous solid solution xLi
2mnO
3. (1-x) LiM ' O2.As M '=Mn
0.5ni
0.5the time, be xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2the rich lithium composite positive pole of layer-layer.Li
2mnO
3have the halite structure, symmetry is C2/m.Can be write as Li[Li
1/3mn
2/3] O
2form is the layer structure of Li layer and manganese layer formation, Li
+and Mn
4+common formation manganese layer, each octahedra Li
+by six octahedra Mn
4+the formation Li (Mn) that surrounds
6structure, and the lithium ion in the Li layer is tetrahedral structure.Li
2mnO
3electro-chemical activity lower, electronic conductivity and ionic conductivity are also very little.As itself and the LiMn that is all layer structure
0.5ni
0.5o
2after compound, form the rich lithium layered cathode material xLi of layered-layered structure
2mnO
3. (1-x) Li Mn
0.5ni
0.5o
2, make the positive electrode of this structure that the discharge capacity over 200mAh/g be arranged.This material is when charging voltage is less than 4.6V, and Mn keeps+4 valencys constant, Li
2mnO
3structure keeps inertia, and the stability of positive electrode structure is provided, and prevents that material structure caves in charge and discharge process, and Ni, from+become+4 valencys of divalent state, is the active component of generation capacity.When charging voltage surpasses 4.6V, in the 4.6V position, will there will be a platform, Li
2o is from Li
2mnO
3deviate from fully in lattice and become MnO
2, more than at this moment cell voltage will reach 4.8V; When battery starts to discharge, the Li before deviate from
2o does not return in lattice, along with the Ni that carries out of electric discharge
4+be reduced to gradually Ni
2+, the Mn in material subsequently
4+also be reduced the participation electrochemical process, so Li
2mnO
3activation while surpassing 4.6V is that this material has the reason [Johnson, C.S., N.Li, et al., Electrochemistry communications, 2007,9 (4): 787-795.] over 200mAh/g.
Yet, xLi in fact
2mnO
3. (1-x) LiM ' O
2the microstructure of the rich lithium layered cathode material of layered-layered structure is very complicated, as Thackeray M.M.[Thackeray M M, Kang S-H, Johnson C S, et al.Journal of Materials Chemistry, 2007,17:3112-3125.] etc. the people point out like that, the result of study of XRD and x ray absorption near edge structure test all shows xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2o
2the rich lithium layered cathode material of layered-layered structure is not pure solid solution, and excessive lithium ion is distributed in transition metal layer by arest neighbors Mn
4+surround, form the LiMn of local cluster
6structure, and LiMn
6li just
2mnO
3feature structure.So xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2material structure is regarded stratiform Li as
2mnO
3with stratiform LiMn
0.5ni
0.5o
2compound on nanoscale, its lithium ion and the arranging shortrange order of transition metal ions and long-range is unordered more suitable.Like this, due to insulation phase Li
2mnO
3existence, Li
2mnO
3the electronic conductivity of feature structure and ionic conductivity are all very low, on the other hand, and xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2laminate Li
2mnO
3interlamellar spacing and LiMn
0.5ni
0.5o
2it is larger that interlamellar spacing differs, and both does not mate the embedding that causes lithium ion and deviate from more difficultly, causes the overall lithium ion conductivity of composite material low, and the lithium ion diffusion coefficient is 10
-12-10
-13s/cm
2between.So xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2cyclical stability not good, repeatedly the circulation after capacity attenuation very fast, when charging and discharging currents increases, capacity attenuation is very fast.
Finishing is a kind of very effective method of improving rich lithium stratiform anode material for compound lithium ion battery cyclical stability and multiplying power property, such as sour preliminary treatment can be xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2in structure, the LiO composition filters out in advance, thereby makes the efficiency for charge-discharge of circulation in first week bring up to [Kang S H, Thackeray M M., Electrochemical Society, 2008,155:A269-A275.] more than 90%.Some oxides are as Al
2o
3, ZrO
2, ZnO, CeO
2[Myung S T, Izumi K, Komaba S, etal.J.Phys.Chem.C, 2007,111 (10): 4061-4067] surface coats the Surface Oxygen activity that can be reduced in rich lithium stratiform anode material for compound lithium ion battery under high voltage, isolated electrode material and electrolyte to a certain extent, slow down the destruction that discharges the effects on surface lattice structure due to HF, thereby improve its cyclic discharge capacity hold facility.But current finishing component only plays the effect of guard electrode surface of active material structure usually, more limited to improving its multiplying power property effect; Thereby and the finishing material does not often have the discharge capacity that electro-chemical activity reduces material monolithic.Therefore further explore the finishing of this positive electrode to developing the high performance xLi of composite lithium-rich anode material layer by layer
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2very important meaning is arranged.The defect sturcture LiFePO4 is as LiFe
0.9p
0.95o
3.775here Fe: the P stoichiometric proportion departs from former 1: 1 stoichiometric proportion slightly, owing to there being micro-Fe in material structure: P mismatch and ionic conductivity is increased sharply.Adopt this material to carry out finishing and can overcome the too low and material electrochemical performance defect that causes of composite lithium-rich anode material ionic conductivity layer by layer.
Summary of the invention
Technical problem to be solved by this invention is layer-layer composite lithium-rich anode material xLi of a kind of defect sturcture LiFePO4 surface modification of providing for existing background technology
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2(0≤x≤0.5).Introduce non-stoichiometric Fe in the LiFePO4 system: P defect sturcture LiFe
1-2yp
1-yo
4-δ, δ is for balancing charge δ=4-[(1-2y) and * 2+1+ (1-y) * 5]/2, y=0.01-0.06 wherein; Ionic conductivity increases substantially, when it is coated to layer-layer composite lithium-rich anode material xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2when (0≤x≤0.5) is upper, be reduced on the one hand the Surface Oxygen activity of rich lithium stratiform anode material for compound lithium ion battery under high voltage, reduced positive electrode has reduced HF release effects on surface lattice structure destruction with contacting of electrolyte; LiFe in addition
1-2yp
1-yo
4-δitself be exactly a kind of positive electrode active materials of higher capacity, be conducive to keep the high power capacity of material monolithic; While Fe
3+/ Fe
2+lower and the good reversibility of oxidation-reduction potential, receive in charging and deviate from and embedding is returned in rich lithium material again lithium ion reduces irreversible capacity loss; Particularly advantageously its high-lithium ion conductivity has greatly been improved the low shortcoming of positive electrode lithium ion conductivity; These factors make layer-layer composite lithium-rich anode material xLi
2mnO3
.(1-x) LiMn
0.5ni
0.5o
2(0≤x≤0.5) has better circulation volume hold facility and multiplying power property.
The present invention reaches by the following technical solutions, and this technical scheme provides the layer of defect sturcture LiFePO4 surface modification-layer composite lithium-rich anode material xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2(0≤x≤0.5); The stoichiometric equation of its surface reforming layer is LiFe
1-2yp
1-yo
4-δ, δ=4-[(1-2y) and * 2+1+ (1-y) * 5]/2, y=0.01-0.06; The 1%-10% that the amount of substance of surface reforming layer is the positive electrode amount.
In this technical scheme, will be according to stoichiometric equation xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2the soluble lithium compounds of (0≤x≤0.5), soluble manganese salt, soluble nickel salt are dissolved in deionized water, and adding amount of substance is that all metal ions total amount 1.2-2.0 tartaric acid doubly stirs to dissolving fully; The temperature of system is risen to 70-85 ℃ and continue to stir until the water evaporation of 70-85%, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground in the baking oven of 130-200 ℃ in mortar to 10-30 minute after dry 20-48 hour.The powder that obtains is warmed up to 500-600 ℃ and at this temperature lower calcination 3-5 hour with the speed of 2-10 ℃/minute in tube furnace, cooling rear taking-up powder, continue to grind 10-30 minute in mortar, with the pressure of 100-300MPa, powder is pressed into to sheet, be warmed up to 850-950 ℃ of calcining 5-15 hour with the speed of 2-10 ℃/minute in tube furnace, obtain lithium-rich anode material after cooling with stove.Will be according to stoichiometric equation LiFe
1-2yp
1-yo
4-δ, wherein: y=0.01-0.06; Soluble lithium compounds, soluble ferrite, ammonium dihydrogen phosphate be dissolved in deionized water at normal temperature and continue and stir, adding amount of substance is that all metal ions total amount 2.5-4.0 tartaric acid doubly stirs to dissolving fully; The lithium-rich anode material that adds 10-100 doubly to measure forms suspension; continuing under the condition stirred; the temperature of rising suspension is to 75-85 ℃; slow evaporation moisture; until system becomes the muddy of thickness; this material is put into after 100-160 ℃ of oven drying 10-20 hour and taken out the speed with 2-10 ℃/minute under the nitrogen atmosphere protection and be warmed up to 600-850 ℃ of calcining 10-15 hour, with the cooling layer-layer composite lithium-rich anode material that obtains defect sturcture LiFePO4 surface modification of stove.Wherein: the solubility lithium salts is LiNO
3, CH
3a kind of in COOLi; Soluble manganese salt is Mn (CH
3cOO)
24H
2o, MnSO
4h
2a kind of in O; Soluble nickel salt is Ni (CH
3cOO)
24H
2o, NiSO
46H
2a kind of in O; Soluble ferric iron salt is Fe (CH
3cOO)
2, Fe (Cl)
24HxO, Fe (NO
3)
26H
2a kind of in O.
Compared with prior art, the invention has the advantages that: as this defect sturcture LiFe
1-2yp
1-yo
4-δbe compound to layer-layer composite lithium-rich anode material xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2when (0≤x≤0.5) is upper, be reduced on the one hand the Surface Oxygen activity of rich lithium stratiform anode material for compound lithium ion battery under high voltage, reduced positive electrode has reduced HF release effects on surface lattice structure destruction with contacting of electrolyte; LiFe in addition
1-2yp
1-yo
4-δitself be exactly a kind of positive electrode active materials of higher capacity, be conducive to keep the high power capacity of material monolithic; While Fe
3+/ Fe
2+lower and the good reversibility of oxidation-reduction potential, receive in charging and deviate from and embedding is returned in rich lithium material again lithium ion reduces irreversible capacity loss; Particularly advantageously its high-lithium ion conductivity has greatly been improved the low shortcoming of positive electrode lithium ion conductivity; These factors make layer-layer composite lithium-rich anode material xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2(0≤x≤0.5) has better circulation volume hold facility and multiplying power property.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by LiNO
3: Mn (CH
3cOO)
24H
2o: Ni (CH
3cOO)
24H
2o=1.1: the ratio of 0.55: 0.45 (mol ratio) is evenly mixed, and is dissolved in deionized water, adds the tartaric acid that amount of substance is 1.2 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 70 ℃ and continue to stir until 71% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 10 minutes after dry 22 hours in the baking oven of 130 ℃ in mortar.The powder that obtains is warmed up to 500 ℃ and this temperature lower calcination 3 hours with the speed of 2 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 10 minutes, with the pressure of 100MPa, powder is pressed into to sheet, then be warmed up to 850 ℃ of calcinings 5 hours with the speed of 2 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.By LiNO
3, Fe (CH
3cOO)
2, ammonium dihydrogen phosphate=be dissolved in deionized water at normal temperature at 1.0: 0.98: 0.99, its total amount of substance is lithium-rich anode material 2%, add the tartaric acid that amount of substance is 2.5 times of all metal ions total amounts to stir to dissolving fully, continue to stir rising system temperature to 70 ℃, above-mentioned lithium-rich anode material powder is joined in clear liquid and forms suspension, slow evaporation moisture, until system becomes the muddy of thickness, this material is put into to 120 ℃ of oven dryings to be taken out after 10 hours with the speed of 2 ℃/minute and is warmed up to 600 ℃ of calcinings 10 hours, with the cooling layer-layer composite lithium-rich anode material that obtains defect sturcture LiFePO4 surface modification of stove.
Embodiment 2: by LiNO
3: Mn (CH
3cOO)
24H
2o: Ni (CH
3cOO)
24H
2o=1.5: the ratio of 0.75: 0.25 (mol ratio) is evenly mixed, and is dissolved in deionized water, adds the tartaric acid that amount of substance is 1.6 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 80 ℃ and continue to stir until 75% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 20 minutes after dry 40 hours in the baking oven of 150 ℃ in mortar.The powder that obtains is warmed up to 550 ℃ and this temperature lower calcination 4 hours with the speed of 5 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 20 minutes, with the pressure of 200MPa, powder is pressed into to sheet, then be warmed up to 900 ℃ of calcinings 5 hours with the speed of 5 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.By CHxCOOLi, Fe (Cl)
24H
2o, ammonium dihydrogen phosphate=be dissolved in deionized water at normal temperature at 1.0: 0.88: 0.94, its total amount of substance is lithium-rich anode material 5%, add the tartaric acid that amount of substance is 4.0 times of all metal ions total amounts to stir to dissolving fully, continue to stir rising system temperature to 85 ℃, slow evaporation moisture, until system becomes the muddy of thickness, this material is put into to 140 ℃ of oven dryings to be taken out after 15 hours with the speed of 6 ℃/minute and is warmed up to 850 ℃ of calcinings 15 hours, with the cooling layer-layer composite lithium-rich anode material that obtains defect sturcture LiFePO4 surface modification of stove.
Embodiment 3: by LiNO
3: Mn (CH
3cOO)
24H
2o: Ni (CH
3cOO)
24H
2o=1.2: the ratio of 0.6: 0.4 (mol ratio) is evenly mixed, and is dissolved in deionized water, adds the tartaric acid that amount of substance is 2.0 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 85 ℃ and continue to stir until 83% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 30 minutes after dry 48 hours in the baking oven of 200 ℃ in mortar.The powder that obtains is warmed up to 600 ℃ and this temperature lower calcination 5 hours with the speed of 10 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 30 minutes, with the pressure of 300MPa, powder is pressed into to sheet, then be warmed up to 950 ℃ of calcining l5 hour with the speed of 9 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.By LiNO
3, Fe (Cl)
24H
2o, ammonium dihydrogen phosphate=be dissolved in deionized water at normal temperature at 1.0: 0.94: 0.97, its total amount of substance is lithium-rich anode material 9%, add the tartaric acid that amount of substance is 3.0 times of all metal ions total amounts to stir to dissolving fully, continue to stir rising system temperature to 80 ℃, above-mentioned lithium-rich anode material powder is joined in clear liquid and forms suspension, at slow evaporation moisture, until system becomes the muddy of thickness, this material is put into to 160 ℃ of oven dryings to be taken out after 20 hours with the speed of 9 ℃/minute and is warmed up to 750 ℃ of calcinings 12 hours, with the cooling layer-layer composite lithium-rich anode material that obtains defect sturcture LiFePO4 surface modification of stove.
Embodiment 4: by CH
3cOOLi: MnSO
4h
2o: Ni (CH
3cOO)
24H
2o=1.5: the ratio of 0.75: 0.25 (mol ratio) is evenly mixed, and is dissolved in deionized water, adds the tartaric acid that amount of substance is 1.8 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 75 ℃ and continue to stir until 75% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 15 minutes after dry 20 hours in the baking oven of 160 ℃ in mortar.The powder that obtains is warmed up to 520 ℃ and this temperature lower calcination 4 hours with the speed of 4 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 10 minutes, with the pressure of 150MPa, powder is pressed into to sheet, then be warmed up to 920 ℃ of calcinings 10 hours with the speed of 8 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.By LiNO
3, Fe (NO
3)
26HxO, ammonium dihydrogen phosphate=be dissolved in deionized water at normal temperature at 1.0: 0.96: 0.98, its total amount of substance is lithium-rich anode material 6%, add the tartaric acid that amount of substance is 3.5 times of all metal ions total amounts to stir to dissolving fully, continue to stir rising system temperature to 78 ℃, above-mentioned lithium-rich anode material powder is joined in clear liquid and forms suspension, slow evaporation moisture, until system becomes the muddy of thickness, this material is put into to 160 ℃ of oven dryings to be taken out after 20 hours with the speed of 9 ℃/minute and is warmed up to 800 ℃ of calcinings 12 hours, with the cooling layer-layer composite lithium-rich anode material that obtains defect sturcture LiFePO4 surface modification of stove.
Embodiment 5: by LiNO
3: Mn (CH
3cOO)
24H
2o: NiSO
46H
2o=1.3: the ratio of 0.65: 0.35 (mol ratio) is evenly mixed, and is dissolved in deionized water, adds the tartaric acid that amount of substance is 1.4 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 78 ℃ and continue to stir until 80% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 15 minutes after dry 40 hours in the baking oven of 180 ℃ in mortar.The powder that obtains is warmed up to 600 ℃ and this temperature lower calcination 5 hours with the speed of 8 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 30 minutes, with the pressure of 250MPa, powder is pressed into to sheet, then be warmed up to 950 ℃ of calcinings 15 hours with the speed of 9 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.By CH
3cOOLi, Fe (Cl)
24H
2o, ammonium dihydrogen phosphate=be dissolved in deionized water at normal temperature at 1.0: 0.94: 0.97, its total amount of substance is lithium-rich anode material 6%, adding amount of substance is all metal ions total amount, 2.8 tartaric acid doubly stirs to dissolving fully, continue to stir rising system temperature to 82 ℃, above-mentioned lithium-rich anode material powder is joined in clear liquid and forms suspension, slow evaporation moisture, until system becomes the muddy of thickness, this material is put into to 160 ℃ of oven dryings to be taken out after 20 hours with the speed of 9 ℃/minute and is warmed up to 780 ℃ of calcinings 13 hours, with the cooling layer-layer composite lithium-rich anode material that obtains defect sturcture LiFePO4 surface modification of stove.
Claims (3)
1. the layer of a defect sturcture LiFePO4 surface modification-layer composite lithium-rich anode material xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2(0≤x≤0.5), the stoichiometric equation of its surface reforming layer is LiFe
1-2yp
1-yo
4-δ, δ=4-[(1-2y) and * 2+1+ (1-y) * 5]/2, y=0.01-0.06; The 1%-10% that the amount of substance of surface reforming layer is the positive electrode amount.
2. the layer of defect sturcture LiFePO4 surface modification according to claim 1-layer composite lithium-rich anode material, is characterized in that preparation process carries out in two steps, at first, will be according to stoichiometric equation xLi
2mnO
3. (1-x) LiMn
0.5ni
0.5o
2the soluble lithium compounds of (0≤x≤0.5), soluble manganese salt, soluble nickel salt are dissolved in deionized water, and adding amount of substance is that all metal ions total amount 1.2-2.0 tartaric acid doubly stirs to dissolving fully, the temperature of rising system continue to stir until the water evaporating liquid of 70-85% becomes thickness and forms gelatin to 70-85 ℃, gelatin material is ground in the baking oven of 130-200 ℃ in mortar to 10-30 minute after dry 20-48 hour, the powder that obtains is warmed up to 500-600 ℃ and at this temperature lower calcination 3-5 hour with the speed of 2-10 ℃/minute in tube furnace, cooling rear taking-up powder, continue to grind 10-30 minute in mortar, with the pressure of 100-300MPa, powder is pressed into to sheet, speed with 2-10 ℃/minute in tube furnace is warmed up to 850-950 ℃ of calcining 5-15 hour, with the cooling lithium-rich anode material that obtains of stove, secondly, will be according to stoichiometric equation LiFe1-2yP1-yO4-δ, wherein: y=0.01-0.06, soluble lithium compounds, soluble ferrite, ammonium dihydrogen phosphate be dissolved in deionized water at normal temperature and continue and stir, adding amount of substance is that all metal ions total amount 2.5-4.0 tartaric acid doubly stirs to dissolving fully, the lithium-rich anode material that adds 10-100 doubly to measure forms suspension, continuing under the condition stirred, the temperature of rising suspension is to 75-85 ℃, slow evaporation moisture, until system becomes the muddy of thickness, this material is put into after 100-160 ℃ of oven drying 10-20 hour and taken out the speed with 2-10 ℃/minute under the nitrogen atmosphere protection and be warmed up to 600-850 ℃ of calcining 10-15 hour, with the cooling layer-layer composite lithium-rich anode material that obtains defect sturcture LiFePO4 surface modification of stove.
3. preparation process according to claim 2, it is characterized in that wherein: the solubility lithium salts is LiNO
3, CH
3a kind of in COOLi; Soluble manganese salt is Mn (CH
3cOO)
24H
2o, MnSO
4h
2a kind of in O; Soluble nickel salt is Ni (CH
3cOO)
24H
2o, NiSO
46H
2a kind of in O; Soluble ferric iron salt is Fe (CH
3cOO)
2, Fe (Cl)
24H
2o, Fe (NO
3)
26H
2a kind of in O.
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|---|---|---|---|
| CN201310022221.4A CN103117385B (en) | 2013-01-05 | 2013-01-05 | A kind of defect sturcture LiFePO4The rich lithium layer-layer positive electrode of surface modification and preparation method |
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| CN103794787A (en) * | 2014-02-21 | 2014-05-14 | 张萍 | Preparation method of high-energy-efficiency positive electrode composite material of lithium ion battery |
| JP2020527832A (en) * | 2017-07-07 | 2020-09-10 | シーエスアイアールＣｓｉｒ | Dual active cathode material |
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| JP2020527832A (en) * | 2017-07-07 | 2020-09-10 | シーエスアイアールＣｓｉｒ | Dual active cathode material |
| JP7295837B2 (en) | 2017-07-07 | 2023-06-21 | シーエスアイアール | dual active cathode material |
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