CN109638275A - A kind of selenium, the nickelic positive electrode of silicate codope and its preparation method and application - Google Patents
A kind of selenium, the nickelic positive electrode of silicate codope and its preparation method and application Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The present invention relates to a kind of selenium, the nickelic positive electrode of silicate codope and its preparation method and application, the positive electrode is the nickelic positive electrode that selenium and silicate co-doped are modified, chemical formula LiNixM1‑xSea(SiO4)bO2‑a‑b, wherein at least one of M Mn, Co or Al, and 0.5≤x <, 1,0 < a≤0.05,0 b≤0.05 <.The present invention carries out anion doped at a low price, improvement material lattice structure to nickelic positive electrode using selenium and silicate；Selenium and silicate have good synergistic effect, can be improved the structural stability of material under high voltages, hence it is evident that improve the chemical property of nickelic positive electrode.Gained positive electrode recycles specific discharge capacity >=185mAh/g under 2.5-4.2V voltage window, 0.1C current density for the first time, and 200 circle capacity retention ratio >=85% of circulation has a good application prospect.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of selenium, silicate codope are nickelic
Positive electrode and its preparation method and application.
Background technique
With greatly developing for new-energy automobile, lithium ion battery industry comes into Rapid development stage.Influence lithium from
The critical material of sub- battery performance mainly has positive electrode, negative electrode material, electrolyte etc..Wherein, positive electrode is to limit at present
The principal element of battery performance, while being also the principal element for accounting for lithium ion battery higher cost, close to 40%.
Positive electrode the most studied in recent years mainly has LiFePO4, LiMn2O4, ternary material etc..Wherein nickelic positive material
Material has advantage more outstanding in terms of cost and comprehensive performance, has been increasingly becoming the technology path of mainstream.
In order to further increase the chemical property of high-nickel material, researcher usually passes through the means such as doping and carries out to material
Modification has many documents and patent report about the doping vario-property of nickelic positive electrode at present both at home and abroad.
Peng Yue etc. first prepares LiNi using coprecipitation0.6Co0.2Mn0.2O2, then again by itself and NH4F is blended in
5h is roasted under the conditions of 450 DEG C obtains the LiNi of F doping0.6Co0.2Mn0.2O2-xFx, experimental result is shown, with the increasing of F doping
Add the reduction of material initial discharge specific capacity, but cyclical stability increases (Yue P, Wang Z, Li X, et al.The
enhanced electrochemical performance of LiNi0.6Co0.2Mn0.2O2cathode materials by
low temperature fluorine substitution.Electrochimica Acta,2013,95:112-118)。
Chunyan Fu etc. prepares (Ni using coprecipitation0.6Co0.2-xMn0.2Mgx)CO3Presoma, then be mixed with out with LiOH
The NCM positive electrode of Mg doping, the more undoped material of the initial discharge specific capacity and cycle performance of material increase (Fu
C,Zhou Z,Liu Y,et al.Synthesis and electrochemical properties of Mg-doped
LiNi0.6Co0.2Mn0.2O2cathode materials for Li-ion battery.Journal of Wuhan
University of Technology-Mater.Sci.Ed.,2011,26(2):211-215).Xu Yuebin etc. uses carbonate
Coprecipitation prepares the Li (Ni of Ti doping0.6Co0.2Mn0.2)1-xTixO2Positive electrode, initial discharge specific capacity are
172.5mAh·g-1, 10 times circulation after specific discharge capacity be 170.5mAhg-1(Xu Yuebin, Zhong Shengkui, Zhang Qian .Ti doping
LiNi0.6Co0.2Mn0.2O2Preparation and chemical property functional material, 2010:295-297).
CN106654210A discloses a kind of nickelic positive electrode of high temperature long circulating lithium ion battery and preparation method thereof, with
Nb is doped chemical, Nb2O5For clad activating oxide, the high rate performance and cycle performance of nickelic positive electrode are improved.
CN105070907A discloses a kind of nickelic positive electrode, matrix surface adulterate Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr,
Ba, Y, Nd, Cs, W, Mo, Ru, Rd or lanthanide series alleviate cleaning solution pair by doped chemical stabilized matrix surface crystal structure
Substrate material surface structural damage keeps the capacity of lithium ion battery of nickelic positive electrode preparation and cycle performance preferable.
Although aforesaid way improves the performance of nickelic positive electrode by doping vario-property, it still has certain limitation
Property, the space that the chemical property of nickelic positive electrode still makes progress.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of selenium, the nickelic positive material of silicate codope
Material and its preparation method and application, further improves the chemical property of nickelic positive electrode by way of codope.
To reach this purpose, the invention adopts the following technical scheme:
In a first aspect, the positive electrode is selenium the present invention provides a kind of selenium, silicate codope nickelic positive electrode
Modified nickelic positive electrode, chemical formula LiNi with silicate co-dopedxM1-xSea(SiO4)bO2-a-b, wherein M Mn,
At least one of Co or Al, and 0.5≤x <, 1,0 < a≤0.05,0 b≤0.05 <.
The present invention carries out anion doped at a low price, a small amount of selenium substitution oxygen original using selenium and silicate to nickelic positive electrode
Son can improve material lattice structure, improve material electronics conductance；In addition, Se can form covalent bond with the Si in silicate,
Inhibit the lattice during removal lithium embedded to collapse, improve material structural stability under high voltages, so be obviously improved it is nickelic just
The chemical property of pole material makes it obtain excellent cyclical stability and capacity retention ratio.
According to the present invention, the range of x is 0.5≤x < 1 in the chemical formula, for example, can be 0.5,0.55,0.6,
0.65, the specific point value between 0.7,0.75,0.8,0.85,0.9,0.95,0.99 or 0.999 etc. and above-mentioned numerical value, is limited to
Length and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the range of a is 0 a≤0.05 < in the chemical formula, for example, can be 0.001,0.005,
0.01, the specific point value between 0.02,0.03,0.04 or 0.05 etc. and above-mentioned numerical value is examined as space is limited and for concise
Consider, the present invention no longer exclusive list.
According to the present invention, the range of b is 0 b≤0.05 < in the chemical formula, for example, can be 0.001,0.005,
0.01, the specific point value between 0.02,0.03,0.04 or 0.05 etc. and above-mentioned numerical value is examined as space is limited and for concise
Consider, the present invention no longer exclusive list.
Second aspect, the present invention provides a kind of selenium, nickelic positive electrodes of silicate codope as described in relation to the first aspect
Preparation method, the described method comprises the following steps:
(1) ingredient is carried out according to the content of each element in chemical formula, nickel source, the source M, selenium is added in cocurrent into reaction vessel
Source, silicon source and precipitating reagent and complexing agent, control temperature and pH value stirring is reacted, and are separated by solid-liquid separation, obtain after the reaction was completed
Positive electrode material precursor；
(2) positive electrode material precursor and the lithium source mixing obtained step (1), obtains the selenium, silicon after Overheating Treatment
The nickelic positive electrode of acid group codope.
The present invention during the preparation process each raw material according to chemical formula LiNixM1-xSea(SiO4)bO2-a-bThe ratio of middle restriction
Carry out ingredient.
According to the present invention, agitating device is had in step (1) described reaction vessel.
According to the present invention, step (1) nickel source is nickel nitrate.
Preferably, step (1) M is at least one of manganese, cobalt or aluminium, correspondingly, the manganese source be manganese chloride and/
Or manganese nitrate；The cobalt source is cobalt nitrate and/or cobalt oxalate；Source of aluminium is aluminum nitrate and/or sodium metaaluminate.
According to the present invention, step (1) selenium source is the hydrazine hydrate solution of selenium.
According to the present invention, step (1) silicon source is the ethanol solution of ethyl orthosilicate.
According to the present invention, step (1) precipitating reagent is sodium hydroxide and/or potassium hydroxide.
According to the present invention, step (1) complexing agent is ammonium hydroxide.
In step (1), the additional amount of precipitating reagent and complexing agent is adjusted all in accordance with actual conditions, as long as control solution
Reaction pH in affiliated range.
According to the present invention, the pH of solution is 10-12.5 in step (1) described reaction process.
According to the present invention, the temperature of step (1) described reaction is 45-75 DEG C, such as can be 45 DEG C, 50 DEG C, 55 DEG C, 60
DEG C, 65 DEG C, 70 DEG C or the specific point value between 75 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
According to the present invention, the time of step (1) described reaction be 4-16h, such as can be 4h, 6h, 8h, 10h, 12h,
Specific point value between 14h or 16h and above-mentioned numerical value, as space is limited and for concise consideration, the no longer exhaustive column of the present invention
It lifts.
According to the present invention, after step (1) described separation of solid and liquid, products therefrom is washed and is dried, obtain it is described just
Pole material precursor.
According to the present invention, step (2) lithium source is lithium carbonate and/or Lithium hydroxide monohydrate.
According to the present invention, the elemental lithium in step (2) described lithium source and the metallic element in the positive electrode material precursor
Molar ratio be (1-1.2): 1, for example, can be 1:1,1.03:1,1.05:1,1.08:1,1.1:1,1.13:1,1.15:1,
Specific point value between 1.18:1 or 1.2:1 and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer
Exclusive list.
Metallic element in the positive electrode material precursor is Ni and metal M.
According to the present invention, step (2) heat treatment carries out in oxygen atmosphere.
According to the present invention, the heating rate of step (2) described heat treatment be 1-30 DEG C/min, such as can be 1 DEG C/min,
It is specific between 5 DEG C/min, 10 DEG C/min, 15 DEG C/min, 20 DEG C/min, 25 DEG C/min or 30 DEG C/min and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (2) heat treatment is divided into two stages progress, the first stage: is sintered at 300-500 DEG C
4-12h；Second stage: the product of first stage is warming up to 600-800 DEG C of sintering 10-20h.
The temperature of above-mentioned first stage heat treatment is 300-500 DEG C, such as can be 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C
Or the specific point value between 500 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the no longer exhaustive column of the present invention
It lifts.
The time of above-mentioned first stage heat treatment is 4-12h, for example, can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or
Specific point value between 12h and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
The temperature of above-mentioned second stage heat treatment is 600-800 DEG C, such as can be 600 DEG C, 630 DEG C, 650 DEG C, 680
DEG C, 700 DEG C, 730 DEG C, 750 DEG C, 780 DEG C or the specific point value between 800 DEG C and above-mentioned numerical value, as space is limited and for letter
Bright consideration, the present invention no longer exclusive list.
The time of above-mentioned second stage heat treatment is 10-20h, for example, can be 10h, 11h, 12h, 13h, 14h, 15h,
Specific point value between 16h, 17h, 18h, 19h or 20h and above-mentioned numerical value, as space is limited and for concise consideration, this hair
Bright no longer exclusive list.
The preparation method packet of selenium of the present invention, the nickelic positive electrode of silicate codope as a preferred technical solution,
Include following steps:
(1) ingredient is carried out according to the content of each element in chemical formula, cocurrent adds into the reaction vessel with agitating device
Enter nickel source, the source M, selenium source, silicon source and precipitating reagent and complexing agent, controlled at 45-75 DEG C, pH value is that 10-12.5 stirring is anti-
4-16h is answered, is separated by solid-liquid separation after the reaction was completed, positive electrode material precursor is obtained；
(2) positive electrode material precursor and the lithium source mixing obtained step (1), controls the elemental lithium and presoma in lithium source
In metallic element molar ratio be (1-1.2): 1, be warming up to 300-500 DEG C under oxygen atmosphere with the rate of 1-30 DEG C/min
It is sintered 4-12h, then proceedes to be warming up to 600-800 DEG C of sintering 10-20h, it is nickelic to obtain the selenium, silicate codope after cooling
Positive electrode.
The third aspect, the present invention provides a kind of selenium, nickelic positive electrodes of silicate codope as described in relation to the first aspect
Application as anode material for lithium-ion batteries.
Compared with prior art, the present invention at least has the advantages that
(1) present invention carries out nickelic positive electrode using selenium and silicate anion doped at a low price, improves material crystalline substance
Lattice structure improves the structural stability of material under high voltages.
(2) selenium and silicate that the present invention adulterates have good synergistic effect, can be obviously improved nickelic positive electrode
Chemical property, gained positive electrode recycles specific discharge capacity under 2.5-4.2V voltage window, 0.1C current density for the first time
>=185mAh/g, 200 circle capacity retention ratio >=85% of circulation.
(3) preparation method provided by the invention is easy to operate, it is easy to accomplish, be conducive to large-scale promotion.
Specific embodiment
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Typical but non-limiting embodiment of the invention is as follows:
Embodiment 1
A kind of selenium, the nickelic positive electrode of silicate codope are present embodiments provided, the chemical formula of the positive electrode is
LiNi0.8Co0.1Mn0.1Se0.02(SiO4)0.05O1.93。
It is prepared in accordance with the following methods:
(1) ingredient is carried out according to the content of each element in chemical formula, cocurrent adds into the reaction vessels with agitating device
Enter the hydrazine hydrate solution of nickel nitrate, cobalt nitrate, the mixed solution of manganese nitrate and selenium and the ethanol solution of ethyl orthosilicate, simultaneously
Appropriate sodium hydroxide solution and ammonium hydroxide is added, controlled at 45 DEG C, pH value is stirred to react 4h for 10, after the reaction was completed solid-liquid point
From obtaining positive electrode material precursor；
(2) positive electrode material precursor for obtaining step (1) and Lithium hydroxide monohydrate mix, control elemental lithium is with before
The molar ratio for driving metallic element in body is that 1.1:1 is warming up to 400 DEG C of burnings then under oxygen atmosphere with the rate of 10 DEG C/min
10h is tied, then proceedes to be warming up to 600 DEG C of heat preservation 20h, cools to room temperature with the furnace after the completion of sintering, obtain selenium, silicate codope
Nickelic positive electrode.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 201mAh/g, 200 circle capacity retention ratios 87% of circulation.
Embodiment 2
A kind of selenium, the nickelic positive electrode of silicate codope are present embodiments provided, the chemical formula of the positive electrode is
LiNi0.6Co0.2Al0.2Se0.01(SiO4)0.02O1.97。
It is prepared in accordance with the following methods:
(1) ingredient is carried out according to the content of each element in chemical formula, cocurrent adds into the reaction vessels with agitating device
Enter the hydrazine hydrate solution of nickel nitrate, cobalt oxalate, the mixed solution of sodium metaaluminate and selenium and the ethanol solution of ethyl orthosilicate, together
When appropriate sodium hydroxide solution and ammonium hydroxide is added, controlled at 75 DEG C, pH value is 12.5 to be stirred to react 4h, solid after the reaction was completed
Liquid separation, obtains positive electrode material precursor；
(2) positive electrode material precursor for obtaining step (1) and lithium carbonate mix control in elemental lithium and presoma
The molar ratio of metallic element is that 1.2:1 is warming up to 300 DEG C of sintering 4h then under oxygen atmosphere with the rate of 20 DEG C/min, so
After be continuously heating to 800 DEG C of heat preservation 10h, cool to room temperature with the furnace after the completion of sintering, obtain selenium, the nickelic anode of silicate codope
Material.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 189mAh/g, 200 circle capacity retention ratios 85% of circulation.
Embodiment 3
A kind of selenium, the nickelic positive electrode of silicate codope are present embodiments provided, the chemical formula of the positive electrode is
LiNi0.7Co0.1Mn0.1Al0.1Se0.05(SiO4)0.03O1.92。
It is prepared in accordance with the following methods:
(1) ingredient is carried out according to the content of each element in chemical formula, cocurrent adds into the reaction vessels with agitating device
Enter the hydrazine hydrate solution of nickel nitrate, cobalt oxalate, manganese nitrate, the mixed solution of sodium metaaluminate and selenium and the ethyl alcohol of ethyl orthosilicate
Solution, while appropriate sodium hydroxide solution and ammonium hydroxide is added, controlled at 60 DEG C, pH value is stirred to react 10h for 11, instead
It should be separated by solid-liquid separation after the completion, obtain positive electrode material precursor；
(2) positive electrode material precursor for obtaining step (1) and Lithium hydroxide monohydrate mix, control elemental lithium is with before
The molar ratio for driving metallic element in body is that 1.05:1 is warming up to 500 DEG C of burnings then under oxygen atmosphere with the rate of 5 DEG C/min
6h is tied, then proceedes to be warming up to 700 DEG C of heat preservation 16h, temperature programmed control is cooled to room temperature after the completion of sintering, and it is total to obtain selenium, silicate
Adulterate nickelic positive electrode.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 194mAh/g, 200 circle capacity retention ratios 86% of circulation.
Embodiment 4
A kind of selenium, the nickelic positive electrode of silicate codope are present embodiments provided, the chemical formula of the positive electrode is
LiNi0.7Mn0.15Al0.15Se0.03(SiO4)0.01O1.96。
It is prepared in accordance with the following methods:
(1) ingredient is carried out according to the content of each element in chemical formula, cocurrent adds into the reaction vessels with agitating device
Enter the hydrazine hydrate solution of nickel nitrate, manganese nitrate, the mixed solution of aluminum nitrate and selenium and the ethanol solution of ethyl orthosilicate, simultaneously
Appropriate sodium hydroxide solution and ammonium hydroxide is added, controlled at 55 DEG C, pH value is stirred to react 12h for 11.5, and reaction is completed
After be separated by solid-liquid separation, obtain positive electrode material precursor；
(2) positive electrode material precursor for obtaining step (1) and Lithium hydroxide monohydrate mix, control elemental lithium is with before
The molar ratio for driving metallic element in body is that 1.03:1 is warming up to 350 DEG C of burnings then under oxygen atmosphere with the rate of 1 DEG C/min
11h is tied, then proceedes to be warming up to 750 DEG C of heat preservation 12h, temperature programmed control is cooled to room temperature after the completion of sintering, and it is total to obtain selenium, silicate
Adulterate nickelic positive electrode.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 195mAh/g, 200 circle capacity retention ratios 87% of circulation.
Embodiment 5
A kind of selenium, the nickelic positive electrode of silicate codope are present embodiments provided, the chemical formula of the positive electrode is
LiNi0.5Co0.3Al0.2Se0.04(SiO4)0.02O1.94。
It is prepared in accordance with the following methods:
(1) ingredient is carried out according to the content of each element in chemical formula, cocurrent adds into the reaction vessels with agitating device
Enter the hydrazine hydrate solution of nickel nitrate, cobalt oxalate, the mixed solution of aluminum nitrate and selenium and the ethanol solution of ethyl orthosilicate, simultaneously
Appropriate potassium hydroxide solution and ammonium hydroxide is added, controlled at 70 DEG C, pH value is stirred to react 6h for 10.5, after the reaction was completed
It is separated by solid-liquid separation, obtains positive electrode material precursor；
(2) positive electrode material precursor for obtaining step (1) and Lithium hydroxide monohydrate mix, control elemental lithium is with before
The molar ratio for driving metallic element in body is that 1.15:1 is warming up to 450 DEG C of burnings then under oxygen atmosphere with the rate of 30 DEG C/min
7h is tied, then proceedes to be warming up to 650 DEG C of heat preservation 18h, temperature programmed control is cooled to room temperature after the completion of sintering, and it is total to obtain selenium, silicate
Adulterate nickelic positive electrode.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 186mAh/g, 200 circle capacity retention ratios 90% of circulation.
Embodiment 6
A kind of selenium, the nickelic positive electrode of silicate codope are present embodiments provided, the chemical formula of the positive electrode is
LiNi0.6Co0.4Se0.01(SiO4)0.02O1.97。
It is prepared in accordance with the following methods:
(1) ingredient is carried out according to the content of each element in chemical formula, cocurrent adds into the reaction vessels with agitating device
Enter the ethanol solution of nickel nitrate, the hydrazine hydrate solution of the mixed solution of cobalt nitrate and selenium and ethyl orthosilicate, while being added suitable
Potassium hydroxide solution and ammonium hydroxide are measured, controlled at 50 DEG C, pH value is stirred to react 14h for 12, after the reaction was completed solid-liquid point
From obtaining positive electrode material precursor；
(2) positive electrode material precursor for obtaining step (1) and lithium carbonate mix control in elemental lithium and presoma
The molar ratio of metallic element is that 1.04:1 is warming up to 450 DEG C of sintering 6h then under oxygen atmosphere with the rate of 15 DEG C/min,
It then proceedes to be warming up to 700 DEG C of heat preservation 16h, program cools to room temperature with the furnace after the completion of sintering, and it is high to obtain selenium, silicate codope
Nickel positive electrode.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 187mAh/g, 200 circle capacity retention ratios 86% of circulation.
Comparative example 1
The chemical formula for the positive electrode that this comparative example provides is LiNi0.8Co0.1Mn0.1(SiO4)0.05O1.95, with embodiment 1
It compares, other than the hydrazine hydrate solution of selenium is not added in step (1), other steps and condition are identical with embodiment 1.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 171mAh/g, 200 circle capacity retention ratios 63% of circulation.
Comparative example 2
The chemical formula for the positive electrode that this comparative example provides is LiNi0.8Co0.1Mn0.1Se0.02O1.98, compared with Example 1,
Other than the ethanol solution of ethyl orthosilicate is not added in step (1), other steps and condition are identical with embodiment 1.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 177mAh/g, 200 circle capacity retention ratios 68% of circulation.
Comparative example 3
The chemical formula for the positive electrode that this comparative example provides is LiNi0.8Co0.1Mn0.1O2, compared with Example 1, in addition to step
Suddenly it is not added in (1) outside the hydrazine hydrate solution of selenium and the ethanol solution of ethyl orthosilicate, other steps and condition and embodiment 1 are completely
It is identical.
Electrochemical property test is carried out using gained positive electrode as anode material for lithium-ion batteries, pole piece proportion is anode
Material: acetylene black: PVDF=90:5:5.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2.5-4.2V voltage
Window, under 0.1C current density, recycling specific discharge capacity for the first time is 169mAh/g, 200 circle capacity retention ratios 59% of circulation.
By embodiment 1-6 it is found that positive electrode prepared by the present invention has excellent chemical property, in 2.5-4.2V
Voltage window under 0.1C current density, recycles specific discharge capacity >=185mAh/g for the first time, and 200 circle capacity retention ratios of circulation >=
85%.By comparative example 1-3 it is found that compared with Example 1, when undope selenium and silicate when, recycle specific discharge capacity for the first time
Only 169mAh/g, 200 circle capacity retention ratio of circulation only has 59%, well below the data in embodiment 1；When only mixing silicate
When (not mixing selenium), the chemical property of nickelic positive electrode is almost without improvement；When only mixing selenium (not mixing silicate), it is nickelic just
The chemical property of pole material makes moderate progress, but it is little to improve amplitude.Illustrate that selenium and silicate have good synergistic effect, energy
Enough chemical properties for improving nickelic positive electrode jointly.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of selenium, the nickelic positive electrode of silicate codope, which is characterized in that the positive electrode is that selenium and silicate are common
The nickelic positive electrode of doping vario-property, chemical formula LiNixM1-xSea(SiO4)bO2-a-b, wherein in M Mn, Co or Al extremely
Few one kind, and 0.5≤x <, 1,0 < a≤0.05,0 b≤0.05 <.
2. the preparation method of selenium as described in claim 1, the nickelic positive electrode of silicate codope, which is characterized in that described
Method the following steps are included:
(1) ingredient is carried out according to the content of each element in chemical formula, nickel source, the source M, selenium source, silicon is added in cocurrent into reaction vessel
Source and precipitating reagent and complexing agent, control temperature and pH value stirring is reacted, and are separated by solid-liquid separation after the reaction was completed, obtain positive material
Material precursor；
(2) positive electrode material precursor and the lithium source mixing obtained step (1), obtains the selenium, silicate after Overheating Treatment
The nickelic positive electrode of codope.
3. method according to claim 2, which is characterized in that have agitating device in step (1) described reaction vessel；
Preferably, step (1) nickel source is nickel nitrate；
Preferably, step (1) M is at least one of manganese, cobalt or aluminium, correspondingly, the manganese source is manganese chloride and/or nitre
Sour manganese；The cobalt source is cobalt nitrate and/or cobalt oxalate；Source of aluminium is aluminum nitrate and/or sodium metaaluminate.
4. method as claimed in claim 2 or claim 3, which is characterized in that step (1) selenium source is the hydrazine hydrate solution of selenium；
Preferably, step (1) silicon source is the ethanol solution of ethyl orthosilicate；
Preferably, step (1) precipitating reagent is sodium hydroxide and/or potassium hydroxide；
Preferably, step (1) complexing agent is ammonium hydroxide.
5. such as the described in any item methods of claim 2-4, which is characterized in that the pH of solution in step (1) described reaction process
For 10-12.5；
Preferably, the temperature of step (1) described reaction is 45-75 DEG C；
Preferably, the time of step (1) described reaction is 4-16h；
Preferably, after step (1) described separation of solid and liquid, products therefrom is washed and is dried, before obtaining the positive electrode
Drive body.
6. such as the described in any item methods of claim 2-5, which is characterized in that step (2) lithium source is lithium carbonate and/or one
Water lithium hydroxide；
Preferably, the molar ratio of the elemental lithium in step (2) described lithium source and the metallic element in the positive electrode material precursor
For (1-1.2): 1.
7. such as the described in any item methods of claim 2-6, which is characterized in that step (2) heat treatment is in oxygen atmosphere
It carries out；
Preferably, the heating rate of step (2) described heat treatment is 1-30 DEG C/min.
8. such as the described in any item methods of claim 2-7, which is characterized in that step (2) heat treatment is divided into two stages
It carries out, the first stage: in 300-500 DEG C of sintering 4-12h；Second stage: the product of first stage is warming up to 600-800 DEG C of burning
Tie 10-20h.
9. such as the described in any item methods of claim 2-8, which is characterized in that the described method comprises the following steps:
(1) ingredient is carried out according to the content of each element in chemical formula, nickel is added in cocurrent into the reaction vessel with agitating device
Source, the source M, selenium source, silicon source and precipitating reagent and complexing agent, controlled at 45-75 DEG C, pH value is that 10-12.5 is stirred to react 4-
16h is separated by solid-liquid separation after the reaction was completed, obtains positive electrode material precursor；
(2) positive electrode material precursor and the lithium source mixing obtained step (1), controls in the elemental lithium and presoma in lithium source
The molar ratio of metallic element is (1-1.2): 1,300-500 DEG C of sintering is warming up to the rate of 1-30 DEG C/min under oxygen atmosphere
4-12h then proceedes to be warming up to 600-800 DEG C of sintering 10-20h, obtains the selenium, the nickelic anode of silicate codope after cooling
Material.
10. selenium as described in claim 1, the nickelic positive electrode of silicate codope answering as anode material for lithium-ion batteries
With.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697221A (en) * | 2020-07-07 | 2020-09-22 | 蜂巢能源科技有限公司 | Doped coated single crystal positive electrode material and method for doping coated single crystal positive electrode material |
| CN112201784A (en) * | 2020-09-28 | 2021-01-08 | 中航锂电技术研究院有限公司 | Positive electrode material, preparation method and application thereof |
| CN112993258A (en) * | 2021-05-12 | 2021-06-18 | 蜂巢能源科技有限公司 | Doping and coating method of ternary cathode material, ternary cathode material and lithium ion battery |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458705A (en) * | 2002-05-13 | 2003-11-26 | 三星Sdi株式会社 | Method for preparing positive active matter of lithium secondary battery |
| US20090117464A1 (en) * | 2007-11-07 | 2009-05-07 | Korea Institute Of Science And Technology | Fabrication method for electrode active material and lithium battery comprising electrode active material fabricated therefrom |
| CN102282098A (en) * | 2008-10-23 | 2011-12-14 | 国立科学研究中心 | Method for producing inorganic compounds |
| KR20130104225A (en) * | 2012-03-13 | 2013-09-25 | 서울대학교산학협력단 | Composite materials for cathode materials in lithium rechargeable battery, methods of manufacturing the same and lithium rechargeable batteries including the same |
| CN103500831A (en) * | 2013-10-22 | 2014-01-08 | 武汉大学 | Manganese-based solid solution positive electrode material doped with anions and preparation method thereof |
| CN104282879A (en) * | 2013-07-03 | 2015-01-14 | 三星Sdi株式会社 | Positive active material, method of preparing the same, and positive electrode for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN106252640A (en) * | 2016-10-24 | 2016-12-21 | 上海电力学院 | A kind of mixing polyanionic lithium manganese silicate anode material and preparation method thereof |
| US20170062813A1 (en) * | 2015-08-25 | 2017-03-02 | Samsung Electronics Co., Ltd. | Composite positive active material, positive electrode and lithium battery containing the composite positive active material |
| US20170179470A1 (en) * | 2015-12-18 | 2017-06-22 | Samsung Electronics Co., Ltd. | Composite positive active material, method of preparing the same, positive electrode including the composite positive active material, and lithium battery including the positive electrode |
| CN107591519A (en) * | 2016-07-06 | 2018-01-16 | 宁德新能源科技有限公司 | Modified lithium nickel cobalt manganese positive electrode material and preparation method thereof |
| CN108336326A (en) * | 2016-12-28 | 2018-07-27 | 株式会社Lg化学 | Positive active material for lithium secondary battery and preparation method thereof and lithium secondary battery |
| CN109360984A (en) * | 2018-12-06 | 2019-02-19 | 济南大学 | A kind of preparation method on layered cathode material of lithium ion battery hydridization surface |
-
2018
- 2018-12-17 CN CN201811545120.4A patent/CN109638275B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458705A (en) * | 2002-05-13 | 2003-11-26 | 三星Sdi株式会社 | Method for preparing positive active matter of lithium secondary battery |
| US20090117464A1 (en) * | 2007-11-07 | 2009-05-07 | Korea Institute Of Science And Technology | Fabrication method for electrode active material and lithium battery comprising electrode active material fabricated therefrom |
| CN102282098A (en) * | 2008-10-23 | 2011-12-14 | 国立科学研究中心 | Method for producing inorganic compounds |
| KR20130104225A (en) * | 2012-03-13 | 2013-09-25 | 서울대학교산학협력단 | Composite materials for cathode materials in lithium rechargeable battery, methods of manufacturing the same and lithium rechargeable batteries including the same |
| CN104282879A (en) * | 2013-07-03 | 2015-01-14 | 三星Sdi株式会社 | Positive active material, method of preparing the same, and positive electrode for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN103500831A (en) * | 2013-10-22 | 2014-01-08 | 武汉大学 | Manganese-based solid solution positive electrode material doped with anions and preparation method thereof |
| US20170062813A1 (en) * | 2015-08-25 | 2017-03-02 | Samsung Electronics Co., Ltd. | Composite positive active material, positive electrode and lithium battery containing the composite positive active material |
| US20170179470A1 (en) * | 2015-12-18 | 2017-06-22 | Samsung Electronics Co., Ltd. | Composite positive active material, method of preparing the same, positive electrode including the composite positive active material, and lithium battery including the positive electrode |
| CN107591519A (en) * | 2016-07-06 | 2018-01-16 | 宁德新能源科技有限公司 | Modified lithium nickel cobalt manganese positive electrode material and preparation method thereof |
| CN106252640A (en) * | 2016-10-24 | 2016-12-21 | 上海电力学院 | A kind of mixing polyanionic lithium manganese silicate anode material and preparation method thereof |
| CN108336326A (en) * | 2016-12-28 | 2018-07-27 | 株式会社Lg化学 | Positive active material for lithium secondary battery and preparation method thereof and lithium secondary battery |
| CN109360984A (en) * | 2018-12-06 | 2019-02-19 | 济南大学 | A kind of preparation method on layered cathode material of lithium ion battery hydridization surface |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697221A (en) * | 2020-07-07 | 2020-09-22 | 蜂巢能源科技有限公司 | Doped coated single crystal positive electrode material and method for doping coated single crystal positive electrode material |
| CN112201784A (en) * | 2020-09-28 | 2021-01-08 | 中航锂电技术研究院有限公司 | Positive electrode material, preparation method and application thereof |
| CN112201784B (en) * | 2020-09-28 | 2022-04-12 | 中创新航技术研究院(江苏)有限公司 | Positive electrode material, preparation method and application thereof |
| CN112993258A (en) * | 2021-05-12 | 2021-06-18 | 蜂巢能源科技有限公司 | Doping and coating method of ternary cathode material, ternary cathode material and lithium ion battery |
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|---|---|
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