CN108615881A - A kind of Li1-（x+y）FeHOxLayPO4Combination electrode material and its technique - Google Patents
A kind of Li1-（x+y）FeHOxLayPO4Combination electrode material and its technique Download PDFInfo
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- CN108615881A CN108615881A CN201611135422.5A CN201611135422A CN108615881A CN 108615881 A CN108615881 A CN 108615881A CN 201611135422 A CN201611135422 A CN 201611135422A CN 108615881 A CN108615881 A CN 108615881A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- 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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- Inorganic Chemistry (AREA)
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- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The object of the present invention is to provide a kind of Li1‑（x+y）FeHOxLayPO4Combination electrode material and its technique.The technique is with FeC2O4・2H2O is as the sources Fe, with Li2CO3As the sources Li, with NH4H2PO4As PO4Source, using Ho, La as doping metals.First by its dispensing by a certain percentage; it is cleaned again with acetone soak; then suitable sucrose is added; ball milling is carried out under the protection of gasoline again; ball milling micro mist dries; it is then charged into the quartz glass tube full of argon gas and seals, place into high temperature furnace and be sintered, taking-up powder in tube to be cooled is up to a kind of combination electrode material after sintering.
Description
Technical field
The present invention relates to a kind of li-ion electrode materials and its preparation process, more particularly to a kind of lithium ion of rare earth element
Electrode material and preparation method thereof belongs to battery electrode material field.
Background technology
In nature, elemental lithium is most light metal, its atomic weight is 6.94g/mol, ρ=0.53g/cm3, electrification
It is minimum to learn equivalent, is 0.26 g Ah-1, standard electrode potential is most negative, is -3.045 V, these features of elemental lithium determine it
It is a kind of material with very high-energy-density, lithium ion battery is exactly this characteristic using elemental lithium, and lithium ion battery is with it
It is higher than energy, operating voltage is high, have extended cycle life, memory-less effect, it is pollution-free the advantages that, in portable electronics and novel traffic
It is widely used in tool.
The selection of material is to influence the first element of performance of lithium ion battery.From the point of view of material angle, the cyclicity of material
Energy factor will restrict the further development of lithium battery, on the one hand may be brilliant in cyclic process in the cyclic process of battery
Body structure change is too fast to take off lithium to continue to complete embedding lithium, on the one hand may be due to active material and corresponding electrolyte without
The SEI films that method generates dense uniform cause active material that side reaction occurs to early with electrolyte and makes the too fast consumption of electrolyte in turn
Influence cycle.Wherein common LiFePO 4 material belongs to newer anode material for lithium-ion batteries, safe, cost compared with
It is low, but that there are room-temperature conductivities is low, and discharge voltage is low（3.4V）, actual capacity only has the shortcomings of 114mAh/g, all constrains
The further application of itself, therefore, exploitation composite positive pole is at one of research direction of anode material for lithium-ion batteries.
LiFePO4With the hexagonal closs packing arrangement architecture slightly distorted, belong to rhombic system, space group Pnma.
Include PO in a-c planes where lithium atom4Tetrahedron, which limits the mobile spaces of lithium ion, therefore it
Conductivity Ratio others lamellar compound is low.There is document to point out, rare earth element can be well dissolved into instead of the position of Li
In olivine structural, and it can change and improve LiFePO4Conductivity.The present invention is adulterated dilute by ball-milling technology, high temperature solid-state method
Native Ho and La atoms, prepare a kind of anode material for compound lithium ion battery, and two kinds of rare earth element compoundings make up pure ferric phosphate lithium electricity
The chemical property performance of the deficiency of pole material, the modified electrode material of this method is excellent, has a good application prospect.
Invention content
The object of the present invention is to provide a kind of Li1-（x+y）FeHOxLayPO4Combination electrode material and its technique.The preparation work
Skill includes the following steps：
(1) the FeC for taking appropriate chemistry pure2O4・2H2O 、Li2CO3、NH4H2PO4With rare earth metal Ho, La powder as raw material, press
According to Li1-（x+y）FeHoxLayPO4（0.01≤x+y≤0.1）Atomic ratio dispensing；
(2) the raw material prepared is poured into acetone soln together, carry out soaking and washing；
(3) the raw mixture after cleaning is further risen in input ball grinder, and add suitable sucrose and steel ball, in gasoline
Under protection, ball milling is carried out with planetary ball mill；
Ball milling for a period of time after, alloy powder is taken out and is dried；
(5) the powder dried is fitted into the quartz glass tube full of argon gas, and sealed；
(6) quartz glass tube is put into high temperature furnace again, is sintered；
(7) to be cooled after being sintered, powder in tube is taken out up to a kind of compound ion electrode material.
Preferentially, step (3) in, the adding proportion of sucrose and raw material is 0.2-0.3, ratio of grinding media to material 15-20.
Preferentially, step (3) in, planetary ball mill speed control 250-350 r/min operation.
Preferentially, step (4) in, the time that ball milling is carried out with planetary ball mill is 20-40h.
Preferentially, step (6) in, sintering temperature be 600-800 DEG C, time control is in 10-15h.
The present invention has following advantages and characteristic：
(1) the electrode material powder electricity rate prepared is high, and capacity is big；
(2) favorable reproducibility, condition are easy to control；
(3) flow is short, easy to operate.
Embodiment one：
The FeC for taking appropriate chemistry pure2O4・2H2O 、Li2CO3、NH4H2PO4With rare earth metal Ho, La powder as raw material, according to
Li0.9FeHo0.01La0.09PO4Atomic ratio dispensing 5g raw material, the raw material prepared is poured into acetone soln together, carry out
Soaking and washing, the raw material after cleaning further rises in input ball grinder, and adds 1.5g sucrose and 100g steel balls, in the protection of gasoline
Under, carry out ball milling with planetary ball mill, ball milling speed is arranged 250 r/min, after ball milling 40h, alloy powder is taken out and is dried in the air
It is dry, the powder dried is fitted into the quartz glass tube full of argon gas and is sealed, quartz glass tube is then put into 600 DEG C of high temperature
15h is sintered in stove, taking-up powder in tube to be cooled is up to a kind of compound ion electrode material after sintering.
Embodiment two：
The FeC for taking appropriate chemistry pure2O4・2H2O 、Li2CO3、NH4H2PO4With rare earth metal Ho, La powder as raw material, according to
Li0.9FeHo0.09La0.01PO4Atomic ratio dispensing 10g raw material, the raw material prepared is poured into acetone soln together, carry out
Soaking and washing, the raw material after cleaning further rises in input ball grinder, and adds 3g sucrose and 150g steel balls, in the protection of gasoline
Under, carry out ball milling with planetary ball mill, ball milling speed is arranged 300 r/min, after ball milling 30h, alloy powder is taken out and is dried in the air
It is dry, the powder dried is fitted into the quartz glass tube full of argon gas and is sealed, quartz glass tube is then put into 700 DEG C of high temperature
13h is sintered in stove, taking-up powder in tube to be cooled is up to a kind of compound ion electrode material after sintering.
Embodiment three：
The FeC for taking appropriate chemistry pure2O4・2H2O 、Li2CO3、NH4H2PO4With rare earth metal Ho, La powder as raw material, according to
Li0.9FeHo0.05La0.05PO4Atomic ratio dispensing 20g raw material, the raw material prepared is poured into acetone soln together, carry out
Soaking and washing, the raw material after cleaning further rises in input ball grinder, and adds 4g sucrose and 300g steel balls, in the protection of gasoline
Under, carry out ball milling with planetary ball mill, ball milling speed is arranged 350 r/min, after ball milling 20h, alloy powder is taken out and is dried in the air
It is dry, the powder dried is fitted into the quartz glass tube full of argon gas and is sealed, quartz glass tube is then put into 800 DEG C of high temperature
10h is sintered in stove, taking-up powder in tube to be cooled is up to a kind of compound ion electrode material after sintering.
Claims (5)
1. a kind of Li1-（x+y）FeHOxLayPO4Combination electrode material, it is characterised in that the preparation process of the electrode material is by following step
It is rapid to carry out：
(1) the FeC for taking appropriate chemistry pure2O4・2H2O 、Li2CO3、NH4H2PO4With rare earth metal Ho, La powder as raw material, according to
Li1-（x+y）FeHoxLayPO4（0.01≤x+y≤0.1）Atomic ratio dispensing；
(2) the raw material prepared is poured into acetone soln together, carry out soaking and washing；
(3) the raw mixture after cleaning is further risen in input ball grinder, and add suitable sucrose and steel ball, in gasoline
Under protection, ball milling is carried out with planetary ball mill；
Ball milling for a period of time after, alloy powder is taken out and is dried；
(5) the powder dried is fitted into the quartz glass tube full of argon gas, and sealed；
(6) quartz glass tube is put into high temperature furnace again, is sintered；
(7) to be cooled after being sintered, powder in tube is taken out up to a kind of compound ion electrode material.
2. a kind of Li as shown in claim 11-（x+y）FeHOxLayPO4Combination electrode material, which is characterized in that step (3)
In, the adding proportion of sucrose and raw material is 0.2-0.3, ratio of grinding media to material 15-20.
3. a kind of Li as shown in claim 11-（x+y）FeHOxLayPO4Combination electrode material, which is characterized in that step (3)
In, planetary ball mill speed control 250-350 r/min operations.
4. a kind of Li as shown in claim 11-（x+y）FeHOxLayPO4Combination electrode material, which is characterized in that step (4)
In, the time that ball milling is carried out with planetary ball mill is 20-40h.
5. a kind of Li as shown in claim 11-（x+y）FeHOxLayPO4Combination electrode material, which is characterized in that step (6)
In, sintering temperature is 600-800 DEG C, and time control is in 10-15h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611135422.5A CN108615881A (en) | 2016-12-11 | 2016-12-11 | A kind of Li1-（x+y）FeHOxLayPO4Combination electrode material and its technique |
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| CN201611135422.5A CN108615881A (en) | 2016-12-11 | 2016-12-11 | A kind of Li1-（x+y）FeHOxLayPO4Combination electrode material and its technique |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428652A (en) * | 2015-12-23 | 2016-03-23 | 郑春燕 | Novel rare-earth-lithium iron phosphate composite electrode material and preparation method thereof |
| CN105514428A (en) * | 2015-12-23 | 2016-04-20 | 邬石根 | Composite electrode material and preparation technology thereof |
| CN105609763A (en) * | 2015-12-23 | 2016-05-25 | 郑春燕 | Rare earth Y doped lithium iron phosphate electrode material and preparation method thereof |
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- 2016-12-11 CN CN201611135422.5A patent/CN108615881A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428652A (en) * | 2015-12-23 | 2016-03-23 | 郑春燕 | Novel rare-earth-lithium iron phosphate composite electrode material and preparation method thereof |
| CN105514428A (en) * | 2015-12-23 | 2016-04-20 | 邬石根 | Composite electrode material and preparation technology thereof |
| CN105609763A (en) * | 2015-12-23 | 2016-05-25 | 郑春燕 | Rare earth Y doped lithium iron phosphate electrode material and preparation method thereof |
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Application publication date: 20181002 |