CN1870332A - Copper phosphate plus plate material for lithium battery and its preparation method - Google Patents

Copper phosphate plus plate material for lithium battery and its preparation method Download PDF

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Publication number
CN1870332A
CN1870332A CNA2006100929437A CN200610092943A CN1870332A CN 1870332 A CN1870332 A CN 1870332A CN A2006100929437 A CNA2006100929437 A CN A2006100929437A CN 200610092943 A CN200610092943 A CN 200610092943A CN 1870332 A CN1870332 A CN 1870332A
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phosphate
lithium battery
copper
plate material
plus plate
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CN100438156C (en
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杨勇
李益孝
龚正良
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Xiamen University
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Xiamen University
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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

Abstract

A method for preparing copper phosphate positive electrode material used on lithium cell includes forming copper phosphate positive electrode material by Cu3 (PO4)2 /C as copper phosphate content being 100 mass%-90 mass% and carbon content being o mass% -10mass%, ball -grinding and mixing copper salt with phosphoric acid in chemical metering ratio to obtain copper phosphate material as chemical formula of Cu3(PO4)2 after heat treatment in high temperature, ball-grinding copper phosphate material with carbon material to obtain copper phosphate/carbon composite material as chemical formula of Cu3( PO4 )2 /C.

Description

Copper phosphate plus plate material for lithium battery and preparation method thereof
Technical field
The present invention relates to a kind of anode material of lithium battery, especially relate to the cupric phosphate (Cu that a kind of lithium battery is used 3(PO 4) 2) positive electrode and preparation method thereof.
Background technology
Lithium battery has been widely used in various portable type electronic products through the development of decades.The positive electrode of present commercial lithium battery mainly contains: sulfur dioxide, thionyl chloride, chlorosulfuric acid, manganese dioxide, ferrous disulfide and vanadic acid silver etc.Sulfur dioxide, thionyl chloride and chlorosulfuric acid positive electrode have very high specific energy, but have serious potential safety hazard, and particularly safety problem is more outstanding under the heavy-current discharge condition.Lithium-manganese dioxide battery and lithium-ferrous disulfide battery have higher specific energy and good safety performance, but heavy-current discharge performance is not good enough.Lithium-vanadic acid silver battery has discharge voltage plateau and excellent storage performance stably, but costs an arm and a leg, and environmental pollution is serious.Therefore, seek cheapness, safety, environmental friendliness and have high-energy-density and the anode material of lithium battery of good high rate performance becomes one of the research focus in lithium battery field.Because phosphate material has stable polyanion skeleton structure thereby has good security performance, (Goodenough has a good application prospect in lithium (ion) battery; John B.; Padhi; Akshaya K.; Nanjundaswamy; K.S.; Masquelier; Christian, Cathode materials for secondary (rechargeable) lithium batteries, U.S. Pat 5,910,382).Yet, at present to the research center of gravity of phosphate material mainly aspect the chargeable lithium battery positive electrode, wherein the most representative is olivine-type LiFePO 4Material (Phospho-olivines as positive-electrodematerials for rechargeable lithium batteries, Journal of the ElectrochemicalSociety, 1997,144:1188-1194; Approaching theoretical capaci ty of LiFePO4 at roomtemperature at high rates, Electrochemical and Solid-State Letters, 2001,4:A170-A172; Improved electrochemical performance of a LiFePO4-based composite cathode, Electro-chimica Acta, 2001,46:3517-3523.).The cupric phosphate material has the good safety energy of polyanion section bar material, and environment is comparatively friendly simultaneously, and is also comparatively cheap, aspect anode material of lithium battery good prospects for application arranged.1997, Idota; Yosio; Yasunami; Shoichiro; Tanaka; Just relate to cupric phosphate (U.S. Pat 5,686,203) in the positive electrode of mentioning in people's such as Mitsutoshi the patent " Non-apueous secondary battery ", but do not see the report of specific embodiment and related data.
Summary of the invention
The objective of the invention is to adopt cupric phosphate as lithium battery anode active material, provide a kind of and under big current condition, can provide copper phosphate plus plate material for lithium battery of height ratio capacity and high-specific-power and preparation method thereof.
Copper phosphate plus plate material for lithium battery of the present invention comprises cupric phosphate and cupric phosphate/carbon composite anode material, can be expressed as Cu 3(PO 4) 2/ C.By mass percentage, the content of cupric phosphate is 100%～90%, the content of compound carbon be 0%～10%.
Its step of the preparation method of copper phosphate plus plate material for lithium battery of the present invention is as follows:
1) presses cupric phosphate chemical composition Cu 3(PO 4) 2, the mantoquita of stoichiometric proportion or Cu oxide and phosphoric acid or the phosphate method by ball milling is mixed back high-temperature heat treatment in air, obtain the cupric phosphate material.
2) with the cupric phosphate material with the material with carbon element ball milling, make cupric phosphate/carbon composite.
In step 1), be Cu: P=(2.9～3.1) by stoichiometric proportion mantoquita or Cu oxide and phosphoric acid or phosphatic content: 2.0.Described mantoquita or Cu oxide are selected from least a in copper nitrate, copper acetate, cupric oxalate, basic copper carbonate and the cupric oxide etc.; Described phosphoric acid or phosphate are selected from least a in phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate etc.Described high-temperature heat treatment temperature is 600～1000 ℃, is preferably 700～900 ℃.The described high-temperature heat treatment time is 3～30h, is preferably 10～20h.
In step 2) in, be 3～15h with cupric phosphate with the material with carbon element ball milling time, rotational velocity is 300～600r/min.Described material with carbon element is selected from least a in acetylene black, hard charcoal, the graphite etc.
Described copper phosphate plus plate material can be used for the positive pole of lithium battery, also can be used for lithium hexafluoro phosphate, lithium perchlorate, hexafluoroarsenate lithium and three fluorocarbons sulfonic acid lithium (LiPF 6, LiCl 4, LiAsF 6And CF 3SO 3Li) be electrolytical lithium battery.
Cupric phosphate electrode of the present invention can adopt the coating method preparation, its concrete steps be by quality than copper phosphate plus plate material: acetylene black: binding agent=80: 10: 10, with copper phosphate plus plate material, acetylene black and binding agent ball milling mixing, be coated on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa.With above-mentioned cupric phosphate electrode is positive pole, and lithium metal is a negative pole, and Cellgard 2400 is a barrier film, 1molL -1LiPF 6EC/DMC solution be electrolyte, be assembled into 2025 button cells, on LAND battery test system (Jin Nuo Electronics Co., Ltd. in Wuhan provides), carry out the constant-current discharge performance test.Discharge cut-off voltage is 1.5V.
Compare with existing technical scheme, the present invention adopts the technical scheme of cupric phosphate as lithium battery anode active material, cupric phosphate and material with carbon element are prepared into composite positive pole, the good conductive property improvement of carbon the intergranular contact electricity of cupric phosphate lead, improved the electrode overall conductance, solved the voltage delay problem of cupric phosphate material at the discharge initial stage.Make prepared lithium battery ground have higher specific energy and high rate performance preferably.With carbon containing 3%Cu 3(PO 4) 2/ C material is an example, at 30mAg -1Discharge capacity reaches 370mAhg under the current density -1At 300mAg -1Discharge capacity remains on 340mAhg under the current density -1, embodied high rate performance preferably.The raw materials used cheapness of the present invention, technology is simple, processing ease, therefore cupric phosphate material of the present invention has high cost performance and market potential preferably.
Description of drawings
Fig. 1 is Cu 3(PO 4) 2The x-ray diffraction pattern of material sample.In Fig. 1, a, 700 ℃ of 10h materials; B, 800 ℃ of 10h materials; C, 900 ℃ of 3h materials; D, 600 ℃ of two steps of (10+10) h are fired material.Abscissa be 2 θ/°, θ is the angle of diffraction, ordinate is intensity (Intensity).
Fig. 2 is the discharge curve of battery among the embodiment 1.In Fig. 2, current density is 30mAg -1
Fig. 3 is the discharge curve of battery among the embodiment 2.In Fig. 3, current density is 30mAg -1
Fig. 4 is the discharge curve of battery among the embodiment 3.In Fig. 4, current density is 30mAg -1
Fig. 5 is the discharge curve of battery among the embodiment 4.In Fig. 5, current density is: a, 30mAg -1B, 300mAg -1
Fig. 6 is the discharge curve of battery among the embodiment 5.In Fig. 6, current density is: a, 30mAg -1B, 300mAg -1
Fig. 7 is the discharge curve of battery among the embodiment 6.In Fig. 7, current density is: a, 30mAg -1B, 300mAg -1
Fig. 8 is the discharge curve of battery among the embodiment 7.In Fig. 8, current density is 30mAg -1
In Fig. 2～8, abscissa is capacity (Capacity)/mAhg -1, ordinate is voltage (Voltage)/V.
Embodiment
Embodiment 1
With 1.19g CuO and 1.15g NH 4H 2PO 4In agate jar, be dispersant with 10ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in chamber type electric resistance furnace, under the air atmosphere, 700 ℃ of heat treatment 10h naturally cool to room temperature, promptly obtain described cupric phosphate material.By quality than cupric phosphate material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains anode for lithium battery.
Embodiment 2
With 5.96g CuO and 5.75g NH 4H 2PO 4In agate jar, be dispersant with 30ml acetone, ball milling 3h (rotational velocity 600r/min).After treating acetone volatilization, transfer in the porcelain boat in chamber type electric resistance furnace, under the air atmosphere, 800 ℃ of heat treatment 10h naturally cool to room temperature, promptly obtain described cupric phosphate material.By quality than cupric phosphate material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains anode for lithium battery.
Embodiment 3
With 11.93g CuO and 11.5g NH 4H 2PO 4In agate jar, be dispersant with 40ml acetone, ball milling 10h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in chamber type electric resistance furnace, under the air atmosphere, 900 ℃ of heat treatment 3h naturally cool to room temperature, promptly obtain described cupric phosphate material.By quality than cupric phosphate material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains anode for lithium battery.
Embodiment 4
With 11.93g CuO and 11.5g NH 4H 2PO 4In agate jar, be dispersant with 40ml acetone, ball milling 10h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in chamber type electric resistance furnace, under the air atmosphere, 600 ℃ of heat treatment 10h naturally cool to room temperature., in agate jar, be dispersant then with 30ml acetone with resulting pressed powder, ball milling 5h (rotational velocity 500r/min) once more.After treating acetone volatilization, transfer in the porcelain boat in chamber type electric resistance furnace, under the air atmosphere, 600 ℃ of heat treatment 10h once more naturally cool to room temperature, promptly obtain described cupric phosphate material.By quality than cupric phosphate material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains anode for lithium battery.
Embodiment 5
Embodiment 4 resultant cupric phosphate material 0.97g and 0.03g acetylene black are mixed, and in agate jar, ball milling 10h (rotational velocity 500r/min) promptly obtains described cupric phosphate/carbon composite.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains anode for lithium battery.
Embodiment 6
Embodiment 4 resultant cupric phosphate material 1.90g and 0.10g acetylene black are mixed, and in agate jar, ball milling 12h (rotational velocity 450r/min) promptly obtains described cupric phosphate/carbon composite.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains anode for lithium battery.
Embodiment 7
Embodiment 4 resultant cupric phosphate material 1.80g and 0.20g acetylene black are mixed, and in agate jar, ball milling 10h (rotational velocity 500r/min) promptly obtains described cupric phosphate/carbon composite.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains anode for lithium battery.
Embodiment 8
The cupric phosphate material that embodiment 1～4 is prepared carries out the powder x-ray diffraction experiment on Panalytical X ' the Pert type powder x-ray diffraction instrument that Dutch Philip company produces.Experiment condition is as follows: the copper target, and λ (Cu K α 1)=1.5406 , tube voltage 40KV, tube current 30mA uses the step-scan mode, 0.0167 ° of step-length, per time in step 10s, sweep limits: 10～90 °.Experimental data as shown in Figure 1, in Fig. 1, a embodiment 1, b embodiment 2, c embodiment 3, d embodiment 4.
Embodiment 9
With embodiment 1～7 prepared electrode is positive pole, and lithium metal is a negative pole, and Cellgard 2400 is a barrier film, 1molL -1LiPF 6EC/DMC solution be electrolyte, be assembled into 2025 button cells, on LAND battery test system (Jin Nuo Electronics Co., Ltd. in Wuhan provides), carry out the constant current discharge performance test.Cut-ff voltage is 1.5V.Current density is 30 or 300mAg -1Test environment is 25 ℃ of constant temperature.Test result is shown in Fig. 2～8.

Claims (10)

1. copper phosphate plus plate material for lithium battery is characterized in that comprising cupric phosphate and cupric phosphate/carbon composite anode material, is expressed as Cu 3(PO 4) 2/ C, by mass percentage, the content of cupric phosphate is 100%～90%, the content of compound carbon be 0%～10%.
2. copper phosphate plus plate material for lithium battery preparation method as claimed in claim 1 is characterized in that its step is as follows:
1) presses cupric phosphate chemical composition Cu 3(PO 4) 2, the mantoquita of stoichiometric proportion or Cu oxide and phosphoric acid or the phosphate method by ball milling is mixed back high-temperature heat treatment in air, obtain the cupric phosphate material;
2) with the cupric phosphate material with the material with carbon element ball milling, make cupric phosphate/carbon composite.
3. copper phosphate plus plate material for lithium battery preparation method as claimed in claim 2 is characterized in that in step 1), is Cu: P=2.9～3.1: 2.0 by stoichiometric proportion mantoquita or Cu oxide and phosphoric acid or phosphatic content.
4. copper phosphate plus plate material for lithium battery preparation method as claimed in claim 2 is characterized in that described mantoquita or Cu oxide are selected from least a in copper nitrate, copper acetate, cupric oxalate, basic copper carbonate and the cupric oxide; Described phosphoric acid or phosphate are selected from least a in phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate.
5. copper phosphate plus plate material for lithium battery preparation method as claimed in claim 2 is characterized in that described high-temperature heat treatment temperature is 600～1000 ℃.
6. copper phosphate plus plate material for lithium battery preparation method as claimed in claim 5 is characterized in that described high-temperature heat treatment temperature is 700～900 ℃.
7. as claim 2 or 5 or 6 described copper phosphate plus plate material for lithium battery preparation methods, it is characterized in that the described high-temperature heat treatment time is 3～30h.
8. as claim 2 or 5 or 6 described copper phosphate plus plate material for lithium battery preparation methods, it is characterized in that the described high-temperature heat treatment time is 10～20h.
9. copper phosphate plus plate material for lithium battery preparation method as claimed in claim 2 is characterized in that in step 2) in, be 3～15h with cupric phosphate with the material with carbon element ball milling time, rotational velocity is 300～600r/min.
10. copper phosphate plus plate material for lithium battery preparation method as claimed in claim 2 is characterized in that in step 2) in, described material with carbon element is selected from least a in acetylene black, hard charcoal, the graphite.
CNB2006100929437A 2006-06-15 2006-06-15 Copper phosphate plus plate material for lithium battery and its preparation method Expired - Fee Related CN100438156C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683701A (en) * 2012-05-25 2012-09-19 厦门大学 Rechargeable lithium battery anode material phosphoric acid copper silver and preparation method thereof
JP2014107225A (en) * 2012-11-29 2014-06-09 Nippon Telegr & Teleph Corp <Ntt> Sodium secondary battery
CN104425818A (en) * 2013-08-29 2015-03-18 合肥杰事杰新材料股份有限公司 Phosphate/single-walled carbon nanotube composite material, preparation method and application
CN107134568A (en) * 2017-05-10 2017-09-05 吉林大学 The two-conductor modification preparation method of lithium ion secondary battery anode material ferrosilicon silicate of lithium
CN107611418A (en) * 2017-09-29 2018-01-19 陕西科技大学 A kind of particles self assemble cubic Cu3(PO4)2/Cu2P2O7The preparation method of combination electrode material
CN107732183A (en) * 2017-09-29 2018-02-23 陕西科技大学 A kind of sodium-ion battery positive material Cu3(PO4)2/Cu2P2O7The preparation method of composite
CN109755489A (en) * 2017-11-08 2019-05-14 中国科学院大连化学物理研究所 A kind of fluorophosphoric acid vanadium sodium/preparation of carbon complex and the application of compound
CN110098400A (en) * 2019-05-24 2019-08-06 陕西科技大学 A kind of sodium-ion battery positive material Cu3(PO4)2The preparation method of/CNTs composite material
CN110120511A (en) * 2019-05-24 2019-08-13 陕西科技大学 A kind of graininess Cu3(PO4)2The method for preparing anode material of lithium-ion battery of/super P
CN110137474A (en) * 2019-05-24 2019-08-16 陕西科技大学 A kind of lithium ion battery cupric phosphate/acetylene black composite positive pole material preparation method
CN111900409A (en) * 2020-08-04 2020-11-06 中国科学院物理研究所 Copper compound material used as lithium battery additive and preparation method and application thereof

Family Cites Families (3)

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US3736184A (en) * 1972-03-29 1973-05-29 Mallory & Co Inc P R Metal phosphate and metal arsenate organic electrolyte cells
US5686203A (en) * 1994-12-01 1997-11-11 Fuji Photo Film Co., Ltd. Non-aqueous secondary battery
US6319632B1 (en) * 1999-11-24 2001-11-20 Japan Storage Battery Co., Ltd. Active material for lithium batteries

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683701A (en) * 2012-05-25 2012-09-19 厦门大学 Rechargeable lithium battery anode material phosphoric acid copper silver and preparation method thereof
CN102683701B (en) * 2012-05-25 2014-10-08 厦门大学 Rechargeable lithium battery anode material phosphoric acid copper silver and preparation method thereof
JP2014107225A (en) * 2012-11-29 2014-06-09 Nippon Telegr & Teleph Corp <Ntt> Sodium secondary battery
CN104425818A (en) * 2013-08-29 2015-03-18 合肥杰事杰新材料股份有限公司 Phosphate/single-walled carbon nanotube composite material, preparation method and application
CN107134568A (en) * 2017-05-10 2017-09-05 吉林大学 The two-conductor modification preparation method of lithium ion secondary battery anode material ferrosilicon silicate of lithium
CN107134568B (en) * 2017-05-10 2019-06-28 吉林大学 The two-conductor modification preparation method of lithium ion secondary battery anode material ferrosilicon silicate of lithium
CN107732183A (en) * 2017-09-29 2018-02-23 陕西科技大学 A kind of sodium-ion battery positive material Cu3(PO4)2/Cu2P2O7The preparation method of composite
CN107611418A (en) * 2017-09-29 2018-01-19 陕西科技大学 A kind of particles self assemble cubic Cu3(PO4)2/Cu2P2O7The preparation method of combination electrode material
CN107732183B (en) * 2017-09-29 2020-01-21 陕西科技大学 Cu for positive electrode material of sodium-ion battery3(PO4)2/Cu2P2O7Method for preparing composite material
CN109755489A (en) * 2017-11-08 2019-05-14 中国科学院大连化学物理研究所 A kind of fluorophosphoric acid vanadium sodium/preparation of carbon complex and the application of compound
CN110098400A (en) * 2019-05-24 2019-08-06 陕西科技大学 A kind of sodium-ion battery positive material Cu3(PO4)2The preparation method of/CNTs composite material
CN110120511A (en) * 2019-05-24 2019-08-13 陕西科技大学 A kind of graininess Cu3(PO4)2The method for preparing anode material of lithium-ion battery of/super P
CN110137474A (en) * 2019-05-24 2019-08-16 陕西科技大学 A kind of lithium ion battery cupric phosphate/acetylene black composite positive pole material preparation method
CN111900409A (en) * 2020-08-04 2020-11-06 中国科学院物理研究所 Copper compound material used as lithium battery additive and preparation method and application thereof
CN111900409B (en) * 2020-08-04 2021-11-16 中国科学院物理研究所 Copper compound material used as lithium battery additive and preparation method and application thereof

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