CN1296284C - Process for preparing nano metal oxide material - Google Patents
Process for preparing nano metal oxide material Download PDFInfo
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- CN1296284C CN1296284C CNB2004100607010A CN200410060701A CN1296284C CN 1296284 C CN1296284 C CN 1296284C CN B2004100607010 A CNB2004100607010 A CN B2004100607010A CN 200410060701 A CN200410060701 A CN 200410060701A CN 1296284 C CN1296284 C CN 1296284C
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Abstract
The present invention relates to a preparation method for nanometer metallic oxide materials. Acrylate and derivants thereof are used as monomers, the monomers and a metallic ionized water solution are mixed, or the monomers and the metallic ionized water solution are mixed with cross linking agents, a uniform stable solution with moderate stickiness is prepared, initiating agents are added, acrylate generates chemical crosslink reaction, a polymer network structure is formed, metallic ions are bonded with carboxylate radicals and are fixed in the microstructure of a polymer network, polymer precursors are obtained by drying, the polymer precursors are burnt after pyrolyzed, and corresponding nanometer metallic oxide materials are obtained. The present invention has the advantages of simple technology, easy control and convenient mass production.
Description
Technical field
The present invention relates to a kind of preparation method of nano metal oxide materials, be specially adapted to make the electrode of lithium ion battery, belong to the chemical material field.
Background technology
Lithium ion battery can satisfy miniaturization, the lightweight requirements of portable type electronic product owing to have high-voltage and high-energy-density characteristic, becomes the auxiliary products of the tool market competitiveness in above-mentioned field.Through in a few years Market Selection and competition, lithium ion battery replaces NI-G, nickel metal hydride battery gradually, becomes " 3C " market (camcorder, computer, main flow cellularphone).
The raising of lithium ion battery performance mainly depends on the improvement of electrode materials and the exploitation of novel material.The employed positive electrode material of lithium ion battery is that transition metal oxide is (as LiCoO at present
2, LiNiO
2, LiMn
2O
4Deng), negative material is graphite-like and tin-based oxide class material, and these materials all have the reversible embedding of lithium ion and deviate from performance, thereby reduce the granularity of material, help to reduce the evolving path and the increase electrochemical reaction interface of ion, thereby improve the utilization ratio and the high rate performance of material at material internal.Nano materials generally adopts sol-gel, CVD (Chemical Vapor Deposition) method, and these methods exist shortcomings such as preparation process is numerous and diverse, processing condition harshness, therefore, develop a kind of technology preparation method simple, the easily nano-metal-oxide of control the development and the performance of lithium ion battery material improved the application prospect with reality.
Summary of the invention:
The purpose of this invention is to provide that a kind of technology is simple, the preparation method of manageable nano metal oxide materials, the gained material has nanoscale, big specific surface area.
Technical scheme of the present invention is: the preparation method of nano metal oxide materials is characterized in that:
With acrylate and derivative thereof is monomer, monomer and the mixing of the metal ion aqueous solution or monomer, the metal ion aqueous solution are mixed with linking agent, make the solution of homogeneous, stable, modest viscosity, add initiator then, make acrylate generation chemical crosslink reaction, form polymer network structure, metal ion and carboxylate radical bonding, and be fixed in the microstructure of polymer network, obtain polymer precursor through oven dry; Polymer precursor is calcination after pyrolysis, promptly obtains corresponding nano metal oxide materials.Institute's synthetic oxide material has uniform phase and narrower size range, and particle scale can reach 50～100nm.
The preparation method of aforesaid nano metal oxide materials is characterized in that in the described polymer precursor:
A, polymer monomer are acrylate and derivative thereof, and its structure is CH
2=C (R
1) COOM, wherein R
1The structure of group is H or CH
3, M is H
+Or NH
4 +Or Li
+, the overall mass fraction of shared polymer precursor material is 5～50wt%;
B, the initiator that is used for initiated polymerization are polyreaction initiators commonly used, be a kind of of hydrogen peroxide, persulphate, persulphate and sulphite or thiosulphate, the overall mass fraction of shared polymer precursor material is 0.01～1.0wt%;
C, linking agent are acrylamide and/or N, N '-methylene-bis (acrylamide), and the overall mass fraction of shared polymer precursor material is greater than 0～1.0wt%;
The metal-salt of d, metal ion is the salt of lithium, aluminium, tin, magnesium, calcium, strontium or gallium, and transition metal salt is the salt of cobalt, nickel, manganese, iron, vanadium, copper, titanium, chromium or zinc, or the mixture of two or more salt wherein, the overall mass fraction of shared polymer precursor material is 50～95wt%; Wherein the negatively charged ion of metal-salt is nitrate radical, chlorion, acetate moiety, hydroxide radical, or two or more anionic mixtures wherein.
The preparation method of aforesaid nano metal oxide materials is characterized in that adopting following processing condition:
A, polymerization: 10～100 ℃ of polymerization temperatures;
B, pyrolysis: polymer precursor is 300-500 ℃ of following pyrolysis;
C, calcination: 400-1000 ℃ of following calcination;
D, calcination time: 2～10 hours.
These processing condition are compared with the common process condition can bring following more benefit:
1, simple, the condition of this method technology is easily controlled, and is convenient to the scale operation nano-substance;
2, starting material are inexpensive, can save industrial cost;
3, high temperature sintering time weak point does not even pass through high temperature sintering, can form the material of complete in crystal formation, thereby has shortened preparation time and reduced energy consumption.
The invention has the advantages that the method that adopts polymerized in-situ, monomer and the polymerization of metal-salt mixing solutions are formed polymeric metal salt, handle through pyrolysis, calcination, preparation has the metal oxide materials of nano-scale.Compare with other preparation methods, this method technology is simple, condition is easily controlled, and ion mixes, and is particularly suitable for preparing many composite oxide of metal and a small amount of adulterated metal oxide materials, and prepared oxide material has uniform phase, narrower size range and nanoscale.And can regulate the granularity of obtained material according to the relative quantity of polymer monomer and metal-salt.Therefore, this method not only can be used to prepare high performance lithium ion battery positive and negative electrode oxide material, and can be widely used in the preparation of other composite oxide materials, thereby provides simpler, practical method for preparing nanometer oxide material.
Description of drawings
Fig. 1 is the high rate performance that the material of the embodiment of the invention 1 is used as anode material for lithium-ion batteries.
Fig. 2, LiNi
0.5Mn
1.5O
2The charging and discharging curve of material.
Fig. 3, Li
4Ti
5O
12The charging and discharging curve of material.
Concrete embodiment
Embodiment 1 lithium ion battery Li[Li
0.12Ni
0.32Mn
0.56] O
2The preparation of nano anode material
With 4.70g LiOHH
2O, 9.30g Ni (NO
3)
26H
2O and 20.04g 50%Mn (NO
3)
2Aqueous solution is made into the uniform aqueous solution, dropwise adds 50mg N again, in N '-methylene-bis (acrylamide) and the acrylic acid mixed solution of 20.75g, after stirring, adds 50mg 4% initiator solution (Na
2SO
3+ K
2S
2O
81: 1wt), at 80 ℃ of following initiated polymerizations, polymkeric substance promptly obtains polymer precursor 120 ℃ of oven dry down then.Polymer precursor at 900 ℃ of following calcination 3h, promptly obtains target product Li[Li then at 450 ℃ of following pyrolysis 5h
0.12Ni
0.32Mn
0.56] O
2
Pyrolysis, calcination temperature and time, can change according to synthetic materials is different.In general, pyrolysis temperature is 300～500 ℃, and calcination temperature is 400～1000 ℃.
Gained Li[Li
0.12Ni
0.32Mn
0.56] O
2Show among the TEM figure of material that this method synthetic material has that uniform grain sizes distributes and nanoscale (～70nm).Fig. 1 is the high rate performance of this material effects anode material for lithium-ion batteries, and as shown in Figure 1, material has high loading capacity (～190mAh/g is under the 50mA/g electric current), even under the current density of 400mA/g, also have higher capacity (～140mAh/g).
Embodiment 2 lithium ion battery LiNi
0.5Mn
1.5O
2The preparation of nano anode material
With 10.20g Li (CH
3COO) H
2O, 14.54g Ni (NO
3)
26H
2O and 36.76g Mn (CH
3COO)
24H
2The O aqueous solution is made into the uniform aqueous solution, dropwise adds 50mg N again, in N '-methylene-bis (acrylamide) and the acrylic acid mixed solution of 21.61g, after stirring, adds 50mg 4% initiator solution (K
2S
2O
8), at 80 ℃ of following initiated polymerizations, polymkeric substance promptly obtains polymer precursor 120 ℃ of oven dry down then.Polymer precursor is at 450 ℃ of following pyrolysis 5h, and at 600 ℃ of following calcination 3h, promptly obtains target product LiNi
0.5Mn
1.5O
2
Gained LiNi
0.5Mn
1.5O
2The TEM figure of material is similar to example 1, and grain graininess is 50nm.Fig. 2 is the discharge performance of this material effects anode material for lithium-ion batteries, and as shown in Figure 2, material has high sparking voltage (4.7V) and higher loading capacity (～120mAh/g is under the 50mA/g current density).
Embodiment 3, lithium ion battery Li
4Ti
5O
12The preparation of nano-electrode material
With 4.20g LiOHH
2O, 128.5g 15%TiCl
3Aqueous solution is made into the uniform aqueous solution, dropwise adds 50mg N again, in N '-methylene-bis (acrylamide) and the acrylic acid mixed solution of 36.03g, after stirring, adds 50mg4% initiator solution (K
2S
2O
8), at 80 ℃ of following initiated polymerizations, polymkeric substance promptly obtains polymer precursor 120 ℃ of oven dry down then.Polymer precursor is at 450 ℃ of following pyrolysis 5h, and at 700 ℃ of following calcination 3h, promptly obtains target product Li
4Ti
5O
12
Gained Li
4Ti
5O
12Material has nanoscale, and loading capacity is 130mAh/g, and good cycle (Fig. 3).
The preparation of embodiment 4, lithium ion battery Sn base oxide nanometer negative material
With 22.6g SnCl
22H
2The O mixing is made into the uniform aqueous solution, dropwise adds 50mg N again, in N '-methylene-bis (acrylamide) and the acrylic acid mixed solution of 14.12g, after stirring, adds 50mg 4% initiator solution (Na
2SO
3+ K
2S
2O
81: 1wt), at 80 ℃ of following initiated polymerizations, polymkeric substance promptly obtains polymer precursor 120 ℃ of oven dry down then.Polymer precursor promptly obtains the target product nano SnO at 450 ℃ of following pyrolysis 5h
2
Gained SnO
2Material has nanoscale, and reversible capacity is 600mAh/g, and good cycle.
Claims (2)
1, the preparation method of nano metal oxide materials is characterized in that:
With acrylate and derivative thereof is monomer, monomer and the mixing of the metal ion aqueous solution or monomer, the metal ion aqueous solution are mixed with linking agent, make the solution of homogeneous, stable, modest viscosity, add initiator then, make acrylate generation chemical crosslink reaction, form polymer network structure, metal ion and carboxylate radical bonding, and be fixed in the microstructure of polymer network, obtain polymer precursor through oven dry; Polymer precursor is calcination after pyrolysis, promptly obtains corresponding nano metal oxide materials;
In the described polymer precursor:
A, polymer monomer are acrylate and derivative thereof, and its structure is CH
2=C (R
1) COOM, wherein R
1The structure of group is H or CH
3, M is H
+Or NH
4 +Or Li
+, the overall mass fraction of shared polymer precursor material is 5～50wt%;
B, the initiator that is used for initiated polymerization are polyreaction initiators commonly used, be a kind of of hydrogen peroxide, persulphate, persulphate and sulphite or thiosulphate, the overall mass fraction of shared polymer precursor material is 0.01～1.0wt%;
C, linking agent are acrylamide and/or N, N '-methylene-bis (acrylamide), and the overall mass fraction of shared polymer precursor material is greater than 0, is less than or equal to 1.0wt%;
The metal-salt of d, metal ion is the salt of lithium, aluminium, tin, magnesium, calcium, strontium or gallium, and transition metal salt is the salt of cobalt, nickel, manganese, iron, vanadium, copper, titanium, chromium or zinc, or the mixture of two or more salt wherein, the overall mass fraction of shared polymer precursor material is 50～95wt%; Wherein the negatively charged ion of metal-salt is nitrate radical, chlorion, acetate moiety, hydroxide radical, or two or more anionic mixtures wherein.
2, the preparation method of nano metal oxide materials as claimed in claim 1 is characterized in that adopting following processing condition:
A, polymerization: 10～100 ℃ of polymerization temperatures;
B, pyrolysis: polymer precursor is 300-500 ℃ of following pyrolysis;
C, calcination: 400-1000 ℃ of following calcination;
D, calcination time: 2～10 hours.
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|---|---|---|---|
| CNB2004100607010A CN1296284C (en) | 2004-08-09 | 2004-08-09 | Process for preparing nano metal oxide material |
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|---|---|---|---|
| CNB2004100607010A CN1296284C (en) | 2004-08-09 | 2004-08-09 | Process for preparing nano metal oxide material |
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| CN1296284C true CN1296284C (en) | 2007-01-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539074A (en) * | 2013-09-11 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of transition metal oxide nanopowder |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368281C (en) * | 2005-12-02 | 2008-02-13 | 大连交通大学 | Preparation method of nanometer metal oxide and composite metal oxide |
| CN100372759C (en) * | 2006-08-25 | 2008-03-05 | 南京大学 | Preparation method of mesopore metal oxide |
| CN101989664B (en) * | 2009-08-06 | 2013-06-19 | 中国科学院宁波材料技术与工程研究所 | Method for synthesizing nano-powder used for solid oxide fuel cell on large scale |
| CN102503417B (en) * | 2011-10-11 | 2014-07-16 | 武汉钢铁(集团)公司 | Preparation method for yttria-partially-stabilized zirconia powder |
| CN102503416A (en) * | 2011-10-11 | 2012-06-20 | 武汉钢铁(集团)公司 | Preparation method of magnesium oxide partially stabilized zirconia powder |
| CN102814183B (en) * | 2012-09-13 | 2014-10-29 | 武汉钢铁(集团)公司 | Preparation method of Mn-Fe-Ti oxide system low-temperature selective catalytic reduction (SCR) catalyst |
| CN102824908B (en) * | 2012-09-13 | 2014-11-05 | 武汉钢铁(集团)公司 | Preparation method of Mn-Ti oxide system low-temperature selective catalytic reduction (SCR) catalyst |
| CN103508483B (en) * | 2013-09-11 | 2016-03-09 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of nano tin oxide powder |
| CN114242969B (en) * | 2021-11-18 | 2024-04-26 | 广州大学 | Layered cobalt-free manganese-based lithium ion battery anode material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237558A (en) * | 1998-05-28 | 1999-12-08 | 中国科学技术大学 | Method for preparing composite metal oxide ceramic powder material by using organic polymerization auxiliary prosess |
| CN1315752A (en) * | 2000-03-30 | 2001-10-03 | 中国科学院物理研究所 | Secondary Li ion battery using colloidal polymer as electrolyte and its preparing process |
| CN1419151A (en) * | 2002-12-06 | 2003-05-21 | 大连新世纪纳米科技股份有限公司 | Resin optical lens containing metal oxide nano particle and making method thereof |
-
2004
- 2004-08-09 CN CNB2004100607010A patent/CN1296284C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237558A (en) * | 1998-05-28 | 1999-12-08 | 中国科学技术大学 | Method for preparing composite metal oxide ceramic powder material by using organic polymerization auxiliary prosess |
| CN1315752A (en) * | 2000-03-30 | 2001-10-03 | 中国科学院物理研究所 | Secondary Li ion battery using colloidal polymer as electrolyte and its preparing process |
| CN1419151A (en) * | 2002-12-06 | 2003-05-21 | 大连新世纪纳米科技股份有限公司 | Resin optical lens containing metal oxide nano particle and making method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539074A (en) * | 2013-09-11 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of transition metal oxide nanopowder |
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