CN109802132A - Positive electrode and preparation method thereof with nanometer rivet arrangement - Google Patents

Positive electrode and preparation method thereof with nanometer rivet arrangement Download PDF

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Publication number
CN109802132A
CN109802132A CN201711136090.7A CN201711136090A CN109802132A CN 109802132 A CN109802132 A CN 109802132A CN 201711136090 A CN201711136090 A CN 201711136090A CN 109802132 A CN109802132 A CN 109802132A
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lithium
positive electrode
nanometer
transition metal
metal
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刘孟
姜阳
任重民
刘健
张胜其
王德宇
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Priority to CN201711136090.7A priority Critical patent/CN109802132A/en
Priority to PCT/CN2018/082256 priority patent/WO2019095615A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

Abstract

The invention discloses a kind of positive electrode and preparation method thereof with nanometer rivet arrangement, the secondary spherical particle that positive electrode is made of the primary particle of multi-element transition metal oxides containing lithium；Nanometer lithium-containing oxides between the primary particle of multi-element transition metal oxides containing lithium by calking in their gaps combines；The present invention can effectively inhibit interface dusting of the anode material for lithium-ion batteries second particle between primary particle, and lithium ion battery is enabled to have high specific capacity, excellent cycle performance and security performance.

Description

Positive electrode and preparation method thereof with nanometer rivet arrangement
Technical field
The present invention relates to lithium battery material technical field, be especially a kind of positive electrode with nanometer rivet arrangement and Preparation method.
Background technique
Lithium ion battery has energy density height, output relative to secondary cells such as traditional lead-acid battery, nickel-metal hydride batteries Voltage is high, self discharge is low, memory-less effect and advantages of environment protection and be widely used and develop.Currently, due to The limitation of synthetic technology, the polynary transition group metallic oxide material containing lithium are mainly the secondary spherical of primary particle aggregation growth Grain.And this secondary spherical material is understood after long-term electrochemistry circulation along the interface dusting between primary particle, so that electrode The electrical contact of storeroom is deteriorated, and internal resistance becomes larger, decays too early so as to cause battery capacity.
To solve the above problems, patent JP11329504A and EP2571083 are respectively on the primary particle surface of positive electrode Acetylene black and carbon fiber are coated, so as to the filled opening when second particle ruptures, continues the electric conductivity for keeping positive electrode, To maintain its cycle performance.However, being coated on the acetylene black on primary particle surface or carbon fiber is only to be filled in primary Between grain, the active force between primary particle is smaller, therefore can only reduce contact internal resistance after second particle dusting, cannot be very Inhibit the dusting of second particle well.
Summary of the invention
The technical problem to be solved by the present invention is to the shortcomings that overcoming the above prior art: providing a kind of can effectively press down Interface dusting of the preparing lithium ion battery positive electrode second particle between primary particle, enables lithium ion battery to have high Specific capacity, excellent cycle performance and positive electrode with nanometer rivet arrangement of security performance and preparation method thereof.
Technical solution of the invention is as follows: a kind of positive electrode with nanometer rivet arrangement, it is by more containing lithium The secondary spherical particle of element/transition metal oxide primary particle composition；The primary particle of multi-element transition metal oxides containing lithium Between combined by nanometer lithium-containing oxides of the calking in their gaps；
The chemical composition of the primary particle of multi-element transition metal oxides containing lithium is Li1+uNixCoyMnzA1-x-y-zO2-μ, In, -0.2≤u≤0.2,0≤x≤1,0≤y≤1,0≤z≤1, x+y+z ≠ 0, -0.2≤μ≤0.3；The A be selected from Cr, One of Mg, Ga, Ti, Fe, Cu, Sr, Ca, K, Na, Zn, Al, V, Sc or a variety of；
The chemical composition of the nanometer lithium-containing oxides is LinMmOq, wherein n+m × (valence state of M)=2q；The M be selected from Y, Zr、Nb、Mo、Ta、La、Mo、Ag、Cd、In、Sn、Sb、Bi、Te、Ba、Hf、Pb、Ce、Pr、Nd、Sm、Eu、Gd、Ho、Er、Tm、Yb One of or it is a variety of.
The nanometer lithium-containing oxides is mutually deposited between the primary particle of multi-element transition metal oxides containing lithium with calking Therefore, there is the positive electrode chemical composition of nanometer rivet arrangement can be expressed as Li1+uNixCoyMnzA1-x-y-zO2-μ- LinMmOq 。
The partial size of the primary particle of multi-element transition metal oxides containing lithium is 50-1000nm, the secondary spherical particle Partial size be 0.5-50 μm.
As advanced optimizing, the partial size of the primary particle of multi-element transition metal oxides containing lithium is 200-700 nm, The partial size of the secondary spherical particle is 10-20 μm.
The nanometer lithium-containing oxides is part calking between the primary particle of multi-element transition metal oxides containing lithium Or complete calking.
As optimization, the molar fraction that the nanometer lithium-containing oxides accounts for entire positive electrode is 0.05-15%.
The present invention also provides a kind of preparation methods of positive electrode with nanometer rivet arrangement, include the following steps:
Polynary transition metal precursor and metal M source combination processing are prepared into the second presoma first, it then will be before described second It drives body to be sintered after mixing with lithium source, be made after pulverizing and sieving；
The combination processing is to be stirred the source metal M and polynary transition metal precursor or the source metal M is settled or adsorbed In polynary transition metal precursor surface；
The polynary transition metal precursor is made of a variety of transistion metal compounds；The transistion metal compound is transition gold One or more of the oxide of category, hydroxide, oxyhydroxide, carbonate；
The hydroxide of oxide, carbonate or metal M that the source the metal M is metal M.The hydroxide of the metal M can PH is adjusted using lye by the soluble-salt of metal M to obtain.
As optimization, specifically comprise the following steps:
1) under inert gas atmosphere, the solution of Ni, Co, Mn salt is added in ammonia spirit, while it is molten that lye adjusting is added Liquid pH value obtains sediment, will obtain polynary transition metal precursor after sediment filtering, washing, drying；Wherein, Ni, Co, Mn Salt is one or more of the soluble-salt of Ni, Co, Mn, one or more of lye NaOH, LiOH, KOH, ammonium hydroxide；
2) polynary transition metal precursor is uniformly mixed with the oxide of metal M, carbonate or the salting liquid of metal M is added Into the reaction kettle equipped with polynary transition metal precursor, pH value is adjusted using lye, the hydroxide of metal M is made to settle or inhale It is attached to the surface of polynary transition metal precursor, obtains the second presoma；
3) second presoma is uniformly mixed with lithium source, is then sintered, is obtained with nanometer in air or oxygen atmosphere The positive electrode of rivet arrangement.
The metal M be Y, Zr, Nb, Mo, Ta, La, Mo, Ag, Cd, In, Sn, Sb, Bi, Te, Ba, Hf, Pb, Ce, Pr, One of Nd, Sm, Eu, Gd, Ho, Er, Tm, Yb or a variety of.
Preferably, the molar ratio 0.98-1.20 of lithium source and second presoma, preferably, sintering temperature is divided into two Section, first segment sintering temperature are 450-700 DEG C, and constant temperature time is 2-24 hours, and second segment sintering temperature is 700-1000 DEG C, are burnt Tying the time is 10-36 hours.
The lithium source is one or more of lithium carbonate, lithium hydroxide, lithium chloride, lithium nitrate, lithium acetate.
The present invention also provides a kind of purposes of positive electrode with nanometer rivet arrangement, can be used for be with carbonate solvent Positive electrode in the lithium ion battery of electrolyte is also acted as with the lithium-ion electric of the solid electrolytes such as oxide, sulfide Positive electrode in pond.
The beneficial effects of the present invention are: the present invention is obtained by the synthetic method simply easily implemented with nanometer rivet arrangement Anode material for lithium-ion batteries, the nanometer lithium-containing oxides in calking primary particle gap can effectively generate lattice deformation or It is secondary to effectively inhibit anode material for lithium-ion batteries to eliminate the deformational stress of anode material for lithium-ion batteries for dislocation Interface dusting of the particle between primary particle, enable lithium ion battery have high specific capacity, excellent cycle performance and Security performance.Using the above method of the invention, the available anode material for lithium-ion batteries with nanometer rivet arrangement, Interface dusting of the anode material for lithium-ion batteries second particle between primary particle can be effectively inhibited, and reduces primary particle Between lithium ion transmission range, enable lithium ion battery that there is high specific capacity, excellent cycle performance and security performance.
Detailed description of the invention
Fig. 1 is the shape appearance figure that positive electrode is prepared in comparative example 1.
Fig. 2 is the shape appearance figure that positive electrode is prepared in embodiment 1.
Fig. 3 is to prepare the shape appearance figure after positive electrode charge and discharge cycles in comparative example 1.
Fig. 4 is to prepare the shape appearance figure after positive electrode charge and discharge cycles in embodiment 1.
Fig. 5 is the transmission electron microscope picture that positive electrode is prepared in comparative example 1.
Fig. 6 is the discharge curve that positive electrode is prepared in comparative example 1 and embodiment 1.
The high rate performance figure of positive electrode is prepared in Fig. 7 comparative example 1 and embodiment 1.
Fig. 8 is the cyclic curve figure that positive electrode is prepared in comparative example 1 and embodiment 1.
Fig. 9 is the discharge curve that positive electrode is prepared in comparative example 2 and embodiment 2.
Figure 10 is the high rate performance figure that positive electrode is prepared in comparative example 2 and embodiment 2.
Figure 11 is the cycle performance figure that positive electrode is prepared in comparative example 2 and embodiment 2.
Figure 12 is the discharge curve that positive electrode is prepared in comparative example 3 and embodiment 3.
Figure 13 is the high rate performance figure that positive electrode is prepared in comparative example 3 and embodiment 3.
Figure 14 is the cycle performance figure that positive electrode is prepared in comparative example 3 and embodiment 3.
Specific embodiment
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact Apply example.
Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources.
Analysis method is as follows in embodiments herein:
Utilize the transmission electron microscope of scanning electron microscope S4800H and Holland the FEI production of Japanese Hitachi production Tecnai F20 carries out pattern test analysis.
Benefit carries out electrochemistry using the LAND electrochemical test system CT2001A of Wuhan Xin Nuo Electronics Co., Ltd. production Performance test analysis.
Positive electrode performance test methods:
By positive electrode and conductive agent acetylene black and binder Kynoar (PVdF) in N-methyl pyrrolidones (NMP) solvent In be uniformly mixed, the mass ratio of positive electrode, conductive agent and binder is 85:10:5, and uniformly mixed slurry is coated in aluminium It on foil, is dried in vacuo 12 hours at 120 DEG C, lithium ion cell positive is made.
It the use of above-mentioned pole piece is anode, using lithium metal as cathode, electrolyte uses the carbonic acid second of 1mol/L lithium hexafluoro phosphate The solution of enester and dimethyl carbonate, diaphragm use 20 microns thick of polyethylene and PP composite material, are assembled into CR2032 Type button lithium ion battery.The button cell being assembled into carries out charge-discharge test, and voltage range is 2.8-4.3 volts.
Comparative example 1
Molar ratio according to Ni, Co, Mn is that 8:1:1 prepares mixed solution, weighs six water nickel nitrates, cobalt nitrate hexahydrate, four respectively The dissolution of 500mL water is added in water manganese nitrate 232.63g, 29.10g, 25.10g.1000mL 5mol/L NaOH solution is prepared, and The ammonia spirit of 1000mL 2mol/L.
In the reaction kettle of argon gas protection, 200mL water is added, by the NaOH solution and 2mol/L of mixed solution and 5mol/L Ammonia spirit simultaneously be added in reaction kettle, solution final pH control in 7-14.After sedimentation, filtration washing will be precipitated, Presoma P1 is obtained after 80 DEG C of drying.
Above-mentioned presoma P1 100g is weighed, weighs Li OH.H according to lithium source and presoma P1 molar ratio 1.052O 47.71g is uniformly mixed with presoma P1, after 550 DEG C are sintered 4 hours, are sintered 12 hours at 850 DEG C, are obtained positive electrode LiNi0.8Co0.1Mn0.1O2, it is labeled as 1#。
Comparative example 2
Molar ratio according to Ni, Co, Mn is that 5:2:3 prepares mixed solution, weighs nickel sulfate hexahydrate, cobalt sulfate, one respectively The dissolution of 500mL water is added in water manganese sulfate 131.42g, 56.22g, 50.70g.1000mL 4mol/L NaOH solution is prepared, and The ammonia spirit of 1000mL 2mol/L.
In the reaction kettle of nitrogen protection, 200mL water is added, by the NaOH solution and 2mol/L of mixed solution and 4mol/L Ammonia spirit simultaneously be added in reaction kettle, solution final pH control 11.5.After sedimentation, filtration washing will be precipitated, Presoma P2 is obtained after 80 DEG C of drying.
Above-mentioned forerunner P2 50g is weighed, weighs LiOH H according to lithium source and presoma molar ratio 1.05:12O 23.94g with Presoma P2 is uniformly mixed, and after 400 DEG C are sintered 6 hours, are sintered 12 hours at 850 DEG C, are obtained LiNi0.5Co0.2Mn0.3O2Material Material is labeled as 2#。
Comparative example 3
Molar ratio according to Ni, Co, Mn is that 1:1:1 prepares mixed solution, weighs nickel sulfate hexahydrate, cobalt sulfate, one respectively The dissolution of 500mL water is added in water manganese sulfate 87.61g, 93.72g, 56.34g.1000mL 4mol/L NaOH solution is prepared, and The ammonia spirit of 1000mL 2mol/L.
In the reaction kettle of nitrogen protection, 200mL water is added, by the NaOH solution and 2mol/L of mixed solution and 4mol/L Ammonia spirit simultaneously be added in reaction kettle, solution final ph control 11.After sedimentation, filtration washing will be precipitated, Presoma P3 is obtained after 80 DEG C of drying.
Above-mentioned presoma P3 50g is weighed, weighs LiOH H according to lithium source and presoma P3 molar ratio 1.05:12O 24.07g is uniformly mixed with presoma P3, after 400 DEG C are sintered 4 hours, are sintered 12 hours at 800 DEG C, are obtained LiNi1/3Co1/ 3Mn1/3O2Material is labeled as 3#。
Embodiment 1
Presoma P1 10g is weighed, with Nb2O5 1.6g is uniformly mixed, and obtains presoma P4；Above-mentioned presoma P4 10g is weighed, is pressed LiOH.H is weighed according to lithium source and presoma P4 molar ratio 1.052O 4.56g is uniformly mixed with presoma P4, small in 650 DEG C of sintering 6 Shi Hou is sintered 12 hours at 900 DEG C, obtains positive electrode, is labeled as 4#。
Embodiment 2
Presoma P2 10g is weighed, 100ml deionized water is added, stirring forms dispersion liquid.1mol/L ammonia spirit is prepared, is weighed 7.04g TaCl5, add 14mL deionized water dissolving.
By TaCl5Solution is added in the dispersion liquid of presoma P2, after addition, adjusts pH to 8.0 ~ 9.0 with ammonium hydroxide, Filtering, washing three times, obtain surface cladding Ta (OH) after 100 DEG C of dryings5Presoma P5.
Above-mentioned presoma P5 10g is weighed, weighs Li OH.H according to lithium source and the ratio of presoma P5 molar ratio 1.2:12O 5.34g is uniformly mixed with presoma P5, is sintered 6 hours at 600 DEG C, is sintered 12 hours at 850 DEG C and is obtained positive electrode, is labeled as 5#。
Embodiment 3
Presoma P3 10g is weighed, with Y2O3 0.66g is uniformly mixed, and obtains presoma P6；Above-mentioned presoma P6 10g is weighed, is pressed LiOH.H is weighed according to lithium source and presoma P6 molar ratio 1.052O 4.56g is uniformly mixed with presoma P6, small in 650 DEG C of sintering 6 Shi Hou is sintered 12 hours at 900 DEG C, obtains positive electrode, is labeled as 6#。
Performance test
Fig. 1,2 are the shape appearance figure of the positive electrode prepared in comparative example 1 and embodiment 1, are schemed by SEM it will be clear that preparing Presoma and positive electrode be spherical second particle that partial size is about 10 microns, the particle is by primary of 200 ~ 500nm Grain composition.
Fig. 3,4 be comparative example 1 and embodiment 1, the middle shape appearance figure prepared after positive electrode charge and discharge cycles, can by SEM figure To find out 1#Second particle cracks after positive electrode charge and discharge cycles, and 3#Positive electrode charge and discharge with nanometer rivet arrangement Second particle integrality is preferable after circulation, does not occur cracking phenomena, i.e. nanometer rivet arrangement can effectively inhibit lithium ion battery Interface dusting of the positive electrode second particle between primary particle.
Fig. 5 is to prepare positive electrode 3 in embodiment 1#Transmission electron microscope picture, LiNbO as we can see from the figure3It is nanocrystalline to fill out Gap forms nanometer rivet arrangement between primary particle.
Fig. 8-14 is comparative example 1, prepares positive electrode in embodiment 1, comparative example 2, embodiment 2, comparative example 3, embodiment 3 Discharge curve, high rate performance curve and cycle performance curve, discharge voltage be 4.3V ~ 2.8V.By comparison as can be seen that tool There is nanometer rivet arrangement anode material for lithium-ion batteries that second particle dusting is effectively inhibited to reduce internal resistance, hence it is evident that improve positive material Discharge capacity, high rate performance and the cycle performance of material.
The above is only feature implementation examples of the invention, are not limited in any way to the scope of the present invention.It is all to use together The technical solution formed Deng exchange or equivalence replacement, all falls within rights protection scope of the present invention.

Claims (10)

1. a kind of positive electrode with nanometer rivet arrangement, it is characterised in that: it is by multi-element transition metal oxides containing lithium The secondary spherical particle of primary particle composition；By calking at it between the primary particle of multi-element transition metal oxides containing lithium Nanometer lithium-containing oxides in gap combine；
The chemical composition of the primary particle of multi-element transition metal oxides containing lithium is Li1+uNixCoyMnzA1-x-y-zO2-μ, wherein- 0.2≤u≤0.2,0≤x≤1,0≤y≤1,0≤z≤1, x+y+z ≠ 0, -0.2≤μ≤0.3；The A be selected from Cr, Mg, Ga, One of Ti, Fe, Cu, Sr, Ca, K, Na, Zn, Al, V, Sc or a variety of；
The chemical composition of the nanometer lithium-containing oxides is LinMmOq, wherein n+m × (valence state of M)=2q；The M be selected from Y, Zr、Nb、Mo、Ta、La、Mo、Ag、Cd、In、Sn、Sb、Bi、Te、Ba、Hf、Pb、Ce、Pr、Nd、Sm、Eu、Gd、Ho、Er、Tm、Yb One of or it is a variety of.
2. the positive electrode according to claim 1 with nanometer rivet arrangement, it is characterised in that: the polynary mistake containing lithium The partial size for crossing metal oxide primary particle is 50-1000nm, and the partial size of the secondary spherical particle is 0.5-50 μm.
3. the positive electrode according to claim 1 with nanometer rivet arrangement, it is characterised in that: the nanometer contains lithia Compound is part calking or complete calking between the primary particle of multi-element transition metal oxides containing lithium.
4. a kind of preparation method of the positive electrode with nanometer rivet arrangement, it is characterised in that: first by polynary transition gold Belong to presoma and metal M source combination processing prepares the second presoma, then after mixing by second presoma and lithium source Sintering is made after pulverizing and sieving；
The combination processing is to be stirred the source metal M and polynary transition metal precursor or the source metal M is settled or adsorbed In polynary transition metal precursor surface；
The polynary transition metal precursor is made of a variety of transistion metal compounds；The transistion metal compound is transition gold One or more of the oxide of category, hydroxide, oxyhydroxide, carbonate；
The hydroxide of oxide, carbonate or metal M that the source the metal M is metal M.
5. the preparation method of the positive electrode according to claim 4 with nanometer rivet arrangement, it is characterised in that: specific Include the following steps:
1) under inert gas atmosphere, the solution of Ni, Co, Mn salt is added in ammonia spirit, while it is molten that lye adjusting is added Liquid pH value obtains sediment, will obtain polynary transition metal precursor after sediment filtering, washing, drying；Wherein, Ni, Co, Mn Salt is one or more of the soluble-salt of Ni, Co, Mn, one or more of lye NaOH, LiOH, KOH, ammonium hydroxide；
2) polynary transition metal precursor is uniformly mixed with the oxide of metal M, carbonate or the salting liquid of metal M is added Into the reaction kettle equipped with polynary transition metal precursor, pH value is adjusted using lye, the hydroxide of metal M is made to settle or inhale It is attached to the surface of polynary transition metal precursor, obtains the second presoma；
3) second presoma is uniformly mixed with lithium source, is then sintered, is obtained with nanometer in air or oxygen atmosphere The positive electrode of rivet arrangement.
6. the preparation method of the positive electrode according to claim 4 or 5 with nanometer rivet arrangement, it is characterised in that: The metal M be Y, Zr, Nb, Mo, Ta, La, Mo, Ag, Cd, In, Sn, Sb, Bi, Te, Ba, Hf, Pb, Ce, Pr, Nd, Sm, Eu, One of Gd, Ho, Er, Tm, Yb or a variety of.
7. the preparation method of the positive electrode according to claim 4 or 5 with nanometer rivet arrangement, it is characterised in that: The lithium source is one or more of lithium carbonate, lithium hydroxide, lithium chloride, lithium nitrate, lithium acetate.
8. the preparation method of the positive electrode according to claim 5 with nanometer rivet arrangement, it is characterised in that: lithium source With the molar ratio 0.98-1.20 of second presoma.
9. the preparation method of the positive electrode according to claim 5 with nanometer rivet arrangement, it is characterised in that: step 3) in, sintering temperature is divided into two sections, and first segment sintering temperature is 450-700 DEG C, and constant temperature time is 2-24 hours, second segment sintering Temperature is 700-1000 DEG C, and sintering time is 10-36 hours.
10. a kind of purposes of the positive electrode with nanometer rivet arrangement, it is characterised in that: can be used for carbonate solvent for electricity The positive electrode in the lithium ion battery of liquid is solved, is also acted as with the lithium ion battery of the solid electrolytes such as oxide, sulfide In positive electrode.
CN201711136090.7A 2017-11-16 2017-11-16 Positive electrode and preparation method thereof with nanometer rivet arrangement Pending CN109802132A (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN112864386A (en) * 2020-12-17 2021-05-28 北京工业大学 Surface treatment method for improving performance of lithium ion battery anode material
CN113964308A (en) * 2021-03-25 2022-01-21 Sk新技术株式会社 Positive electrode active material for lithium secondary battery and lithium secondary battery comprising same

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