CN108470907A - A kind of potassium ion doping lithium-rich anode material and preparation method thereof and the application in lithium ion battery - Google Patents
A kind of potassium ion doping lithium-rich anode material and preparation method thereof and the application in lithium ion battery Download PDFInfo
- Publication number
- CN108470907A CN108470907A CN201810225322.4A CN201810225322A CN108470907A CN 108470907 A CN108470907 A CN 108470907A CN 201810225322 A CN201810225322 A CN 201810225322A CN 108470907 A CN108470907 A CN 108470907A
- Authority
- CN
- China
- Prior art keywords
- lithium
- anode material
- preparation
- potassium
- mixed solution
- 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
Classifications
-
- 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
- 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
- H01M4/52—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
-
- 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
Abstract
The invention discloses a kind of potassium ions to adulterate lithium-rich anode material and preparation method thereof and the application in lithium ion battery.The preparation method is：Sodium carbonate and ammonium hydroxide are configured to mixed solution 1, nickel source, cobalt source and manganese source are configured to mixed solution 2, mixed solution 1 is added in the mixed solution 2 of lasting stirring again, it is filtered, washed after reaction, dries to obtain presoma, presoma is mixed with lithium source, potassium resource again, grinding, calcining obtain the lithium-rich anode material of potassium ion doping.Resulting materials of the present invention are Li1.2‑ xKxNi0.2Co0.08Mn0.52O2, when being used for lithium ion cell positive, there is excellent chemical property, in 100mAg‑1Current density under cycle 200 circle, remain to keep 262 mAhg‑1High power capacity, and in 1000mAg‑1High current density under 200 circle of cycle, reversible capacity remains able to reach 153 mAhg‑1。
Description
Technical field
The invention belongs to lithium ion battery material technical fields, and in particular to a kind of potassium ion doping lithium-rich anode material and
Preparation method and the application in lithium ion battery.
Background technology
Currently, the aggravation of environmental problem makes the efficient highly desirable exploitation of people, cleaning and novel energy can be recycled.
Rechargeable lithium ion batteries receive the extensive concern of people as one of green energy resource.It designs, synthesis has high power capacity, good
Good high rate performance, long circulation life and cheap anode material of lithium battery is important one of the developing direction of lithium ion battery.
Rich lithium material is one of most promising anode material for lithium-ion batteries, with high theoretical capacity (~280mAh g-1), high electricity
Flattening bench (>3.5V), the features such as cheap, environmental-friendly, by the extensive favor of people.
In rich lithium material lithium ion in ordered arrangement formed lithium layer, in lithium layer doping with lithium ion property similar in potassium from
Son, since potassium ion radius ratio lithium ion is big, the spacing after adulterating potassium ion between lithium layer becomes larger, and it is de- to be more advantageous to lithium ion
Go out and is embedded in, meanwhile, the structure of stabilizing material is capable of in potassium ion doping after entering, it is thus possible to improve the electrochemistry of material
Energy.Engineer of the present invention has synthesized the lithium-rich anode material of potassium ion doping to improve the chemical property of material.
Some researches show that doping sodium ion can increase the spacing of lithium layer in lithium ion material to improve the multiplying power of material
Performance.Wei He et al. have synthesized the lithium-rich anode material of sodium ion doping using Polymer-pyrolysis method, and are applied to lithium
Ion battery positive electrode has 139mAhg under the multiplying power of 8C-1Reversible capacity, cycle 100 circle after capacity retention ratio be
89%.
The present invention successfully synthesizes the lithium-rich anode material of potassium ion doping by simple coprecipitation technology.When for
When anode material for lithium-ion batteries, potassium ion, which adulterates lithium-rich anode material, has very high specific capacity and excellent cycle performance,
In 100mA g-1Current density under 200 circle of cycle, remain to keep 262mA h g-1Reversible capacity.In 1000mA g-1Electricity
200 circle of cycle, still there is 153mA h g under current density-1Reversible capacity.The present invention is with simple for process, at low cost, environment is friendly
The advantages such as good, efficient, can be with large-scale industrial application.
Invention content
In order to make up for the deficiencies of the prior art, primary and foremost purpose of the present invention is to provide a kind of potassium ion doping lithium-rich anode material
Material.
Another object of the present invention is to provide the low cost of above-mentioned potassium ion doping lithium-rich anode material, high efficiency, can advise greatly
Method prepared by mould.
Still a further object of the present invention is to provide above-mentioned potassium ion and adulterates lithium-rich anode material as high performance lithium ion battery just
The application of pole material.
The object of the invention is achieved through the following technical solutions.
A kind of preparation method of potassium ion doping lithium-rich anode material, includes the following steps：
(1) sodium carbonate and ammonium hydroxide are configured to mixed solution 1, nickel source, cobalt source and manganese source is configured to mixed solution 2, then
Mixed solution 1 is added in the mixed solution 2 of lasting stirring, is filtered, washed after reaction, is dried to obtain carbonate precursor；
(2) carbonate precursor being mixed with lithium source, potassium resource, is ground, calcining obtains potassium ion doping lithium-rich anode material,
Labeled as Li1.2-xKxNi0.2Co0.08Mn0.52O2。
Preferably, the nickel source is one or more of nickel sulfate, nickel acetate, nickel nitrate.
It is preferable that the cobalt source is one or more of cobaltous sulfate, cobalt acetate, cobalt nitrate, cobalt chloride.
Preferably, the manganese source is one or more of manganese sulfate, manganese acetate, manganese nitrate.
It is further preferred that the nickel source is nickel acetate, cobalt source is cobalt acetate, and manganese source is manganese acetate.
Preferably, the mixing speed of the mixed solution 2 is 200~600rpm.Stirring mainly has following two effects：
(1) nickel, cobalt, manganese is made to be uniformly mixed；(2) reaction product is made to spread out, suitable, the good material of crystal form with obtained granular size
Material.In above-mentioned preparation method, the main purpose of washing is to clean the foreign ion on presoma surface, and the purpose of calcining is to provide admittedly
Temperature needed for the diffusion of phase ion.
It is further preferred that the mixing speed of the mixed solution 2 is 400rpm.
Preferably, the lithium source be lithium carbonate, lithium hydroxide more than one.
Preferably, the potassium resource be potassium carbonate, potassium hydroxide more than one.
It is further preferred that the lithium source is lithium carbonate, potassium resource is potassium hydroxide.
Preferably, it is described calcining be first risen to again after 4~6h of pre-burning at 400~600 DEG C 800~950 DEG C calcining 10~
20h.It is further preferred that the calcining is first to rise to 900 DEG C of calcining 15h after pre-burning 5h again at 450 DEG C.
Preferably, Li1.2-xKxNi0.2Co0.08Mn0.52O2Ranging from the 0.006~0.06 of middle x.
It is further preferred that Li1.2-xKxNi0.2Co0.08Mn0.52O2Ranging from the 0.012~0.036 of middle x.
It is highly preferred that Li1.2-xKxNi0.2Co0.08Mn0.52O2Middle x is 0.024.
A kind of potassium ion doping lithium-rich anode material made from above-described preparation method.
A kind of application of the above-described potassium ion doping lithium-rich anode material as anode material for lithium-ion batteries.
Preferably, the above concrete application process is：Potassium ion is adulterated into lithium-rich anode material, acetylene black and PVDF and mixes system
Slurry, is coated on aluminium foil, obtains lithium ion cell positive.
It is further preferred that the application process is：Weigh 0.2g potassium ions doping lithium-rich anode material, 0.0235g second
Acetylene black, 0.0118g PVDF are transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated with by magnetic agitation 2h
Electrode is made on aluminium foil, is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode.
Compared with prior art, the invention has the advantages that and advantageous effect：
(1) present invention uses simple coprecipitation technology, has synthesized potassium ion doping lithium-rich anode material and successfully by it
Applied to anode material for lithium-ion batteries.Potassium ion is doped into the lithium layer of material, since potassium ion radius ratio lithium ion is big, so
Doping potassium ion increases the spacing of lithium layer, is more advantageous to the deintercalation of lithium ion；Potassium ion is not joined in charge and discharge process simultaneously
With react, to stabilize the structure of material, thus improve the chemical property of material.
(2) the raw material nickel source used in the present invention, cobalt source, manganese source, potassium resource are cheap, and the method used in the present invention is
Coprecipitation can be synthesized largely.In addition to this, the present invention is also simple for process, it is pollution-free the features such as.Thus, the present invention
Potential with large-scale industrial production.
(3) when potassium ion of the invention doping lithium-rich anode material is used for lithium ion cell positive with high specific capacity and
Good cycle performance：The Li1.2-xKxNi0.2Co0.08Mn0.52O2In material when ranging from the 0.006~0.06 of x,
Current density is 100mAg-1When, reversible capacity is 201~262mAh g after cycle 50~200 is enclosed-1, it is seen that prepared by the present invention
Potassium ion, which adulterates lithium-rich anode material, has very high specific capacity and good cycle performance, and applying can in lithium ion battery
High-energy density and long-life are provided.
(4) when the potassium ion of present invention doping lithium-rich anode material is used for lithium ion anode, the Li1.2- xKxNi0.2Co0.08Mn0.52O2Middle x ranging from 0.012~0.036 when, current density be 1000mA g-1When 200 circle of cycle,
Reversible capacity is 132~153mAh g-1, it is seen that potassium ion doping lithium-rich anode material prepared by the present invention can adapt to larger electricity
Stream provides safeguard for the application of high-power lithium ion battery.
Description of the drawings
Fig. 1 is the XRD diagram that 5 gained potassium ion of embodiment adulterates lithium-rich anode material.
Fig. 2 is the SEM figures that 6 gained potassium ion of embodiment adulterates lithium-rich anode material.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
100mL deionized waters form mixed solution 2, mixed solution 1 are added in the mixed solution 2 persistently stirred, mixing speed is
200rpm reacts 15h, is filtered, washed, is dried to obtain presoma, then weigh 4.4112g lithium carbonates and 0.0337g potassium hydroxide
It is mixed together, grinds with presoma, then rise to calcining 20h at 800 DEG C after pre-burning 6h at 400 DEG C and obtain the rich lithium of potassium ion doping
Positive electrode.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Embodiment 2
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
100mL deionized waters form mixed solution 2, mixed solution 1 are added in the mixed solution 2 persistently stirred, mixing speed is
400rpm reacts 15h, is filtered, washed, is dried to obtain presoma, then weigh and take 4.3447g lithium carbonates and 0.1346g hydroxides
Potassium is mixed together with presoma, grinds, then rises to calcining 15h at 850 DEG C after pre-burning 5h at 500 DEG C and obtain potassium ion doping richness
Lithium anode material.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Embodiment 3
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
100mL deionized waters form mixed solution 2, mixed solution 1 are added in the mixed solution 2 persistently stirred, mixing speed is
200rpm reacts 15h, is filtered, washed, is dried to obtain presoma, then weigh 4.4112g lithium carbonates and 0.0337g potassium hydroxide
It is mixed together, grinds with presoma, then rise to calcining 15h at 900 DEG C after pre-burning 5h at 450 DEG C and obtain the rich lithium of potassium ion doping
Positive electrode.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Embodiment 4
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
Deionized water forms mixed solution 2, mixed solution 1 is added in the mixed solution 2 persistently stirred, mixing speed 200rpm,
15h is reacted, is filtered, washed, is dried to obtain presoma, then weigh 4.3891g lithium carbonates and 0.0673g potassium hydroxide and presoma
It is mixed together, grinds, then rise to calcining 15h at 900 DEG C after pre-burning 5h at 450 DEG C and obtain potassium ion doping lithium-rich anode material
Material.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Embodiment 5
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
Deionized water forms mixed solution 2, mixed solution 1 is added in the mixed solution 2 persistently stirred, mixing speed 400rpm,
15h is reacted, is filtered, washed, is dried to obtain presoma, then weigh 4.3447g lithium carbonates and 0.1346g potassium hydroxide and presoma
It is mixed together, grinds, then rise to calcining 15h at 900 DEG C after pre-burning 5h at 450 DEG C and obtain potassium ion doping lithium-rich anode material
Material.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Embodiment 6
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
Deionized water forms mixed solution 2, mixed solution 1 is added in the mixed solution 2 persistently stirred, mixing speed 400rpm,
15h is reacted, is filtered, washed, is dried to obtain presoma, then weigh 4.3004g lithium carbonates and 0.2020g potassium hydroxide and presoma
It is mixed together, grinds, then rise to calcining 15h at 900 DEG C after pre-burning 5h at 450 DEG C and obtain potassium ion doping lithium-rich anode material
Material.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Embodiment 7
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
Deionized water forms mixed solution 2, mixed solution 1 is added in the mixed solution 2 persistently stirred, mixing speed 400rpm,
15h is reacted, is filtered, washed, is dried to obtain presoma, then weighs 4.2561g lithium carbonates and 0.3317g potassium carbonate and presoma one
Mixing, grinding are played, then rises to calcining 15h at 900 DEG C after pre-burning 5h at 450 DEG C and obtains potassium ion doping lithium-rich anode material.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Embodiment 8
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
Deionized water forms mixed solution 2, mixed solution 1 is added in the mixed solution 2 persistently stirred, mixing speed 600rpm,
15h is reacted, is filtered, washed, is dried to obtain presoma, then weighs 4.2117g lithium carbonates and 0.4146g potassium carbonate and presoma one
Mixing, grinding are played, then rises to calcining 15h at 900 DEG C after pre-burning 5h at 450 DEG C and obtains potassium ion doping lithium-rich anode material.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Embodiment 9
It weighs 10.1750g sodium carbonate to be dissolved in 100mL deionized waters, is added 3mL 25wt%~28wt%'s thereto
Concentrated ammonia liquor forms mixed solution 1, then weighs 4.9772g nickel acetates, 1.9928g cobalt acetates successively, and 12.7447g manganese acetates are dissolved in
100mL deionized waters form mixed solution 2, mixed solution 1 are added in the mixed solution 2 persistently stirred, mixing speed is
600rpm reacts 15h, is filtered, washed, is dried to obtain presoma, then weigh 4.4112g lithium carbonates and 0.0337g potassium hydroxide
It is mixed together, grinds with presoma, then rise to calcining 10h at 950 DEG C after pre-burning 4h at 600 DEG C and obtain the rich lithium of potassium ion doping
Positive electrode.
Weigh potassium ion doping lithium-rich anode material, 0.0235g acetylene blacks, the 0.0118g obtained by 0.2g the present embodiment
PVDF is transferred in vial after mixed grinding, and 1ml NMP are added, and material is coated on aluminium foil and electricity is made by magnetic agitation 2h
Pole is used as using lithium metal and is assembled into CR2016 type button cells in glove box to electrode, and carries out electrochemical property test.
Performance test：
The material use X-ray diffraction technology (XRD) of above-described embodiment preparation, is swept Raman spectrum (Raman Spectra)
Electron microscope (SEM), transmission electron microscope (TEM) are retouched as characterization method, it is formed, pattern is analyzed.Wherein,
The XRD diagram that 5 gained potassium ion of embodiment adulterates lithium-rich anode material is as shown in Figure 1.The rich lithium of 6 gained potassium ion of embodiment doping is just
The SEM figures of pole material are as shown in Figure 2.The main diffraction peak of material all corresponds to rich lithium material, and diffraction well as shown in Figure 1
Peak is very sharp, illustrates that the rich lithium material crystallinity of potassium ion doping that the present invention synthesizes is high.The particle of material is presented as shown in Figure 2
It is polyhedron-shaped, illustrate that material crystal form is perfect, while particle size distribution is more uniform, range is between 0.5~1.5 μm.
Battery prepared by above-described embodiment is soft using cell tester (the new prestige in Shenzhen) and BTS7.5.5 after shelving 12h
Part, test temperature are room temperature, are 100mAg in current density-1~1000mAg-1In the case of, constant current charge and discharge is carried out to it
Electricity, voltage range are 2.5~4.6V, test the cycle performance and high rate performance of battery.The chemical property of sample refers to table 1.
Cyclic voltammetry (CV) and ac impedance measurement (EIS) are carried out to it using electrochemical workstation (CHI660E, Shanghai Chen Hua).
Table 1
The present invention is prepared for potassium ion using coprecipitation and adulterates lithium-rich anode material, by change mixing speed and potassium from
The ratio chemical property that carrys out the synthesis condition of research material, and have studied respective material of son doping include specific discharge capacity,
Cycle performance and high rate performance etc..As shown in Table 1, by comparing 9 embodiments, it is found that when speed of agitator be 400rpm, x values are
Sample when 0.012~0.036 has good cycle performance, in 100mA g-1Current density under cycle 100~200 circle,
It can keep 210~262mAh g-1High power capacity, especially x be 0.024 when sample cycle 200 circle after, reversible capacity is still
So up to 262mAh g-1, while it is in high current density (1000mA g-1) under cycle 200 circle, still have 153mAh g-1Can
Inverse capacity.
Embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not limited by above-described embodiment
System, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of potassium ion doping lithium-rich anode material, which is characterized in that include the following steps：
（1）Sodium carbonate and ammonium hydroxide are configured to mixed solution 1, nickel source, cobalt source and manganese source are configured to mixed solution 2, then will mix
It closes solution 1 to be added in the mixed solution 2 of lasting stirring, is filtered, washed after reaction, is dried to obtain carbonate precursor；
（2）Carbonate precursor is mixed with lithium source, potassium resource, is ground, calcining obtains potassium ion doping lithium-rich anode material, label
For Li1.2-xKxNi0.2Co0.08Mn0.52O2。
2. preparation method according to claim 1, which is characterized in that step（1）The nickel source be nickel sulfate, nickel acetate and
One or more of nickel nitrate；The cobalt source is one or more of cobaltous sulfate, cobalt acetate, cobalt nitrate and cobalt chloride.
3. preparation method according to claim 1, which is characterized in that step（1）The manganese source be manganese sulfate, manganese acetate and
One or more of manganese nitrate.
4. preparation method according to claim 1, which is characterized in that step（1）The speed of the stirring is 200 ~ 600
rpm。
5. preparation method according to claim 1, which is characterized in that step（2）The lithium source is lithium carbonate and hydroxide
Lithium more than one.
6. preparation method according to claim 1, which is characterized in that step（2）The potassium resource is potassium carbonate and hydroxide
Potassium more than one.
7. preparation method according to claim 1, which is characterized in that step（2）The calcining is first at 400 ~ 600 DEG C
800 ~ 950 DEG C of 10 ~ 20 h of calcining are risen to after 4 ~ 6 h of pre-burning again.
8. preparation method according to claim 1, which is characterized in that step（2）The Li1.2- xKxNi0.2Co0.08Mn0.52O2Ranging from the 0.006 ~ 0.06 of middle x.
9. a kind of potassium ion doping lithium-rich anode material made from claim 1-8 any one of them preparation methods.
10. application of a kind of potassium ion doping lithium-rich anode material as anode material for lithium-ion batteries described in claim 9,
It is characterized in that, concrete application process is：Potassium ion is adulterated into lithium-rich anode material, acetylene black and PVDF mixed pulps, then is applied
Cloth obtains lithium ion cell positive on aluminium foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810225322.4A CN108470907A (en) | 2018-03-19 | 2018-03-19 | A kind of potassium ion doping lithium-rich anode material and preparation method thereof and the application in lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810225322.4A CN108470907A (en) | 2018-03-19 | 2018-03-19 | A kind of potassium ion doping lithium-rich anode material and preparation method thereof and the application in lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108470907A true CN108470907A (en) | 2018-08-31 |
Family
ID=63265479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810225322.4A Pending CN108470907A (en) | 2018-03-19 | 2018-03-19 | A kind of potassium ion doping lithium-rich anode material and preparation method thereof and the application in lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108470907A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110797527A (en) * | 2019-10-23 | 2020-02-14 | 昆明理工大学 | Modified lithium-rich manganese-based oxide cathode material and preparation method thereof |
| CN112479268A (en) * | 2020-11-28 | 2021-03-12 | 海南大学 | Preparation method of hydrogen peroxide-potassium permanganate modified ternary cathode material for lithium ion battery |
| CN112786875A (en) * | 2020-12-30 | 2021-05-11 | 华南理工大学 | Potassium ion doped carbon-coated lithium-rich ternary positive electrode material and preparation method and application thereof |
| CN114835100A (en) * | 2022-04-26 | 2022-08-02 | 上海兰钧新能源科技有限公司 | Preparation method of lithium battery positive electrode material and lithium battery positive electrode material |
| CN114940520A (en) * | 2022-06-24 | 2022-08-26 | 蜂巢能源科技股份有限公司 | Cobalt-free lithium-rich material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413931A (en) * | 2013-08-08 | 2013-11-27 | 北京大学 | Boron-doped lithium-rich anode material for lithium ion batteries and preparation method of material |
| CN103682316A (en) * | 2013-12-20 | 2014-03-26 | 哈尔滨工业大学 | Method for preparing ternary anode material of long-service-life and high-capacity lithium ion battery |
-
2018
- 2018-03-19 CN CN201810225322.4A patent/CN108470907A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413931A (en) * | 2013-08-08 | 2013-11-27 | 北京大学 | Boron-doped lithium-rich anode material for lithium ion batteries and preparation method of material |
| CN103682316A (en) * | 2013-12-20 | 2014-03-26 | 哈尔滨工业大学 | Method for preparing ternary anode material of long-service-life and high-capacity lithium ion battery |
Non-Patent Citations (3)
| Title |
|---|
| WEI HE ET AL.: "Enhanced high-rate capability and cycling stability of Na-stabilized layered Li1.2[Co0.13Ni0.13Mn0.54]O2 cathode material", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| ZHENJIANG HE ET AL.: "Electrochemical performance of zirconium doped lithium rich layered Li1.2Mn0.54Ni0.13Co0.13O2 oxide with porous hollow structure", 《JOURNAL OF POWER SOURCES》 * |
| ZUGUANGYANG ET AL.: "K-doped layered LiNi0.5Co0.2Mn0.3O2 cathode material：Towards the superior rate capability and cycling performance", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110797527A (en) * | 2019-10-23 | 2020-02-14 | 昆明理工大学 | Modified lithium-rich manganese-based oxide cathode material and preparation method thereof |
| CN112479268A (en) * | 2020-11-28 | 2021-03-12 | 海南大学 | Preparation method of hydrogen peroxide-potassium permanganate modified ternary cathode material for lithium ion battery |
| CN112786875A (en) * | 2020-12-30 | 2021-05-11 | 华南理工大学 | Potassium ion doped carbon-coated lithium-rich ternary positive electrode material and preparation method and application thereof |
| CN114835100A (en) * | 2022-04-26 | 2022-08-02 | 上海兰钧新能源科技有限公司 | Preparation method of lithium battery positive electrode material and lithium battery positive electrode material |
| CN114835100B (en) * | 2022-04-26 | 2023-11-17 | 上海兰钧新能源科技有限公司 | Preparation method of lithium battery positive electrode material and lithium battery positive electrode material |
| CN114940520A (en) * | 2022-06-24 | 2022-08-26 | 蜂巢能源科技股份有限公司 | Cobalt-free lithium-rich material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
| CN105655577B (en) | A kind of method that wet method mixes lithium improvement anode material for lithium-ion batteries high temperature solid state reaction | |
| CN108470907A (en) | A kind of potassium ion doping lithium-rich anode material and preparation method thereof and the application in lithium ion battery | |
| CN104659359B (en) | A kind of lithium ion cell nano piece is overlapped piles up cube Mn(3‑x)CoxO4The preparation method of negative material | |
| CN105226264B (en) | A kind of sodium-ion battery richness sodium positive electrode and preparation method thereof and sodium-ion battery | |
| CN105609745A (en) | Nickel selenide/graphene sodium ion battery composite negative material as well as preparation method and application thereof | |
| CN103943848B (en) | The preparation method of the bar-shaped structure cobalt-base anode material for lithium-ion batteries of a kind of porous | |
| CN103280574A (en) | Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material | |
| CN103762354B (en) | A kind of LiNi0.5Mn1.5O4 material, its preparation method and lithium ion battery | |
| CN109301207A (en) | A kind of surface layer doping Ce3+And surface layer coats CeO2NCM tertiary cathode material and preparation method thereof | |
| CN107394164A (en) | Tertiary cathode material and preparation method thereof | |
| CN105140494A (en) | Biomimetic synthesis method of Fe3O4/Fe/C nano composite battery electrode material | |
| CN104362333B (en) | A kind of lithium ion battery preparation method of spherical lithium-rich anode material | |
| CN110190265A (en) | A kind of preparation method of antimony-antimony oxide/redox graphene composite material | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN115057485A (en) | Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof | |
| CN108598409A (en) | A kind of lithium ion battery negative material FeS/Fe/C and preparation method thereof | |
| CN106848297A (en) | The preparation method of rich lithium tertiary cathode material in lithium ion battery | |
| CN108598463B (en) | Preparation method of nano flaky lithium-rich manganese-based positive electrode material | |
| CN104037416A (en) | Preparation method for electrode with three-dimensional structure formed by coating nickel sulfide by fold graphene through self-repairing | |
| CN104485441B (en) | A kind of quaternary metal phosphate anode material for lithium-ion batteries and preparation method thereof | |
| CN106129400A (en) | A kind of lanthanum part replaces spherical lithium-rich manganese-based anode material of manganese and preparation method thereof | |
| CN106129355A (en) | The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium | |
| CN106784750A (en) | A kind of TiO/C negative materials and its preparation method and application | |
| CN104300136B (en) | One-dimensional manganese oxide/carbon coaxial hollow nanorod as well as preparation method and application of nanorod |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180831 |