CN102881865B - Method for manufacturing positive plate of battery - Google Patents
Method for manufacturing positive plate of battery Download PDFInfo
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- CN102881865B CN102881865B CN201210343207.XA CN201210343207A CN102881865B CN 102881865 B CN102881865 B CN 102881865B CN 201210343207 A CN201210343207 A CN 201210343207A CN 102881865 B CN102881865 B CN 102881865B
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- pole piece
- lithium
- group
- lead plate
- battery lead
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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
The invention discloses a method for manufacturing a positive plate of a battery. The method comprises the following steps of: 1, mixing and pulping anhydrous iron phosphate, an adhesive, a conductive agent and a solvent to prepare stable slurry, and coating and drying the stable slurry on an aluminum foil tape to prepare the positive plate; 2, electrochemically treating the positive plate obtained by the step 1, wherein an electrochemical treatment solution contains lithium nitrate and lithium hydroxide; and 3, performing de-ionized water washing, drying and compaction on the lithium nitrate and the lithium hydroxide-containing positive plate obtained by the step 2 to prepare a lithium iron phosphate positive plate. According to the method for manufacturing the positive plate of the battery, an electrochemical method is used for directly synthesizing the iron phosphate into lithium iron phosphate without production equipment and production conditions, which are required by the conventional synthesis of the lithium iron phosphate, so that the cost of materials is lowered, continuous batch production is facilitated, the cycle of a synthetic preparation process is greatly shortened compared with the production cycle of the conventional synthetic preparation process, production efficiency is improved, and economic benefits are further improved.
Description
Technical field
The present invention relates to anode pole piece manufacturing technology field, particularly a kind of manufacture method of lithium-ion battery lithium iron phosphate anode pole piece.
Background technology
Ferric phosphate lithium cell has the advantages such as long-life, safe and reliable, excellent performance, rich material resources, platform stable and memory-less effect because of it, become in recent years the focus that people pay close attention to, its related industry development rapidly, range of application obtains popularizing very greatly, has become domestic important important industry field.The core technology of ferric phosphate lithium cell is the manufacture of battery anode slice.Anode pole piece can be with the poly-inclined to one side tetrafluoroethene of PVDF() or water soluble adhesive as bonding agent, add after conductive agent and active material, make slurry, be coated on aluminium foil and make.The traditional operating procedure of anode pole piece is: the positive electrode active material material of first making ferric phosphate lithium cell is LiFePO4, then dry, batching, slurrying, coating, then through a series of pole pieces of being processed into such as oven dry, compacting, cut-parts.
Above-mentioned anode pole piece preparation process is very ripe, and is extensively adopted by domestic and international producer.But wherein there are a lot of problems: on the one hand, the process of synthesizing iron lithium phosphate need be reacted in special installation, often these equipment millions of units at most of hundreds of thousands unit at least, then add regular maintenance expense, improve to a great extent the cost of positive electrode; On the other hand, need to provide the particular surroundings such as high temperature, protective gas atmosphere in above-mentioned building-up process, these conditions have all increased the synthetic harsh conditions of real material undoubtedly, are difficult to grasp, and have caused the unstable of LiFePO 4 material performance.Traditionally preparation technology's production cycle of LiFePO 4 material longer, only sintering process just reaches tens hours time of tens hours even, has reduced economic benefit.In fact, current domestic LiFePO 4 material unstable properties is an industry difficult problem.
The technical process that how to simplify the operation, reduces energy resource consumption, thereby reduces equipment investment and reduce the manufacturing cost of battery, and having become each enterprise both at home and abroad needs problem demanding prompt solution.
Summary of the invention
(1) technical problem that will solve
The technical problem to be solved in the present invention is, for the deficiencies in the prior art, the invention provides a kind of manufacture method of lithium-ion battery lithium iron phosphate anode pole piece, realize and simplify ferric phosphate positive pole pole piece production process, reduce it and produce upper great number equipment investment, reduce in its production process the energy, resource consumption.
(2) technical scheme
The invention provides a kind of cell positive pole piece making method, comprise the following steps:
S1: anhydrous iron phosphate is mixed to making beating with binding agent, conductive agent and solvent, make stable slurry, coating in aluminium foil strip, oven dry, make anode pole piece;
S2: the anode pole piece in S1 is carried out to electrochemical treatments, and electrochemical treatments solution contains lithium nitrate and lithium hydroxide;
S3: by carrying out washed with de-ionized water, oven dry, compacting containing the anode pole piece of lithium nitrate and lithium hydroxide in S2, make iron phosphate lithium positive pole pole piece.
Wherein, in S1, the percentage by weight of anhydrous iron phosphate is: 30%～50%; Binding agent is Kynoar, and its percentage by weight is: 1%～10%; The percentage by weight of conductive agent is: 1%～10%; Solvent is 1-METHYLPYRROLIDONE, and its percentage by weight is: 30%～68%.
Wherein, described conductive agent is one or more in super carbon black, conductive carbon black, carbon fiber or carbon nano-tube.
Wherein, in S2, in electrochemical treatments solution, the percentage by weight of lithium nitrate is 5%～25%.
Wherein, in S2, in electrochemical treatments solution, hydroxyl is identical with the content of the consumption ion of lithium ion.
Wherein, in S2, the time that described anode pole piece carries out electrochemical treatments is 10～30 hours.
Wherein, carry out in electrochemical processing cell in the electrochemical treatments described in S2, first group of battery lead plate and second group of battery lead plate are set in described electrochemical processing cell, every group of upper and lower corresponding setting of battery lead plate, the relative pole piece voltage of described first group of battery lead plate is-1.0V～-1.2V that the relative pole piece voltage of described second group of battery lead plate is-1.7V～-2V; Described electrode slice is first through first group of battery lead plate, then through second group of battery lead plate.
Wherein, S2 also comprises: in described electrochemical processing cell, pass into electric current 10～20 hours, current density is all to change the ferric phosphate on described anode pole piece into LiFePO4 as standard.
(3) beneficial effect
Cell positive pole piece making method of the present invention adopts electrochemical process, directly ferric phosphate is synthesized to LiFePO4, wherein adopt anhydrous iron phosphate, make LiFePO4 building-up process highly stable, also make the highly stable traditional synthesis of having upgraded of battery performance, without the needed production equipment of traditional synthesizing iron lithium phosphate and working condition, reduce to a great extent equipment investment, reduce the cost of material, be convenient in enormous quantities, serialization is produced, the synthetic synthetic preparation process production cycle of preparation process period ratio tradition significantly shortens, improve production efficiency, thereby further improve economic benefit.
Brief description of the drawings
Fig. 1 is cell positive pole piece making method block diagram of the present invention;
Fig. 2 is electrochemical processing cell structure principle chart of the present invention;
Fig. 3 is anode pole piece manufacture process schematic diagram of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
As shown in Figure 1, the invention provides a kind of cell positive pole piece making method, comprise the following steps:
S1: anhydrous iron phosphate is mixed to making beating with binding agent, conductive agent and solvent, make stable slurry, coating in aluminium foil strip, oven dry, make anode pole piece 3;
S2: the anode pole piece in S1 3 is carried out to electrochemical treatments, and electrochemical treatments solution contains lithium nitrate and lithium hydroxide;
S3: by carrying out washed with de-ionized water, oven dry, compacting containing the anode pole piece 3 of lithium nitrate and lithium hydroxide in S2, make iron phosphate lithium positive pole pole piece 3.
Wherein, in S1, the percentage by weight of anhydrous iron phosphate is: 30%～50%; Binding agent is Kynoar, and its percentage by weight is: 1%～10%; The percentage by weight of conductive agent is: 1%～10%; Solvent is 1-METHYLPYRROLIDONE (NMP), and its percentage by weight is: 30%～68%, and described conductive agent is one or more in super carbon black, conductive carbon black, carbon fiber or carbon nano-tube.
Wherein, in S2, in electrochemical treatments solution, the percentage by weight of lithium nitrate is 5%～25%; In electrochemical treatments solution, hydroxyl is identical with the content of the consumption ion of lithium ion; The time that described anode pole piece 3 carries out electrochemical treatments is 10～30 hours; Described electrochemical treatments is carried out in electrochemical processing cell 5, at interior first group of battery lead plate 1 and the second group of battery lead plate 2 of arranging of described electrochemical processing cell 5, every group of upper and lower corresponding setting of battery lead plate, the relative pole piece voltage of described first group of battery lead plate 1 is-1.0V～-1.2V that the relative pole piece voltage of described second group of battery lead plate 2 is-1.7V～-2V; Described electrode slice is first through first group of battery lead plate 1, then through second group of battery lead plate 2.In addition, S2 also comprises: in described electrochemical processing cell 5, pass into electric current 10～20 hours, current density is all to change the ferric phosphate on described anode pole piece 3 into LiFePO4 as standard.
As shown in Figures 2 and 3, in electrochemical processing cell 5, be full of lithium nitrate solution.First, by interior electrochemical processing cell 5 energising, the pending anode pole piece 3 that prepared early stage first passes into electrochemical processing cell 5.In energising situation, anode pole piece 3 is negative pole, and lithium ion, to the diffusion of pole piece place, enters ferric phosphate lattice, and the ferric ion (Fe3+) in ferric phosphate obtains an electronics and becomes ferrous ion (Fe2+), and then generates LiFePO4 (LiFePO4).Meanwhile, on positive source pole plate, hydroxide ion (OH-) loses electronics, produces oxygen, and reaction equation is:
4OH
--4e
-→2H
2O+O
2↑ （1）
Anode pole piece 3 is by region of discharge, first by first group of battery lead plate 1, then by second group of battery lead plate 2.Through first group of battery lead plate 1(low pressure treatment region), its effect is that to utilize low-voltage to complete most electrochemistry synthetic, now voltage low, polarize littlely, contribute to the abundant diffusion of lithium ion; Described second group of battery lead plate 2(HIGH PRESSURE TREATMENT district) voltage is slightly high, and deep layer diffusion can be carried out by lithium ion in higher-pressure region under high voltage, can further strengthen lithium ion and insert effect.But because voltage is higher, pole piece is had to damage, therefore can not all adopt high voltage.
Aluminium strip enters electrolyte to start, and above reaction is constantly carried out, until the ferric phosphate on anode pole piece 3 aluminium strips all generates LiFePO4.Need to calculate according to the size of electric current the consumption of lithium ion in electrolyte.In fact electrolyte is a process that constantly consumes lithium hydroxide, need to be by continuous supplemental hydrogen lithia, maintain the stable of bath composition.
Because the foreign ions such as nitrate anion are contained in electrolyte the inside, therefore must remove, remove impurity by washed with de-ionized water in subsequent process operation.As shown in Figure 2, anode pole piece 3 cleans twice by rinse bath (6,7), can reach requirement.The pole piece aluminium strip of processing through above-mentioned synthetic, cleaning etc., through operations such as ovens dry, compactings, can be made into the anode pole piece 3 that can be used for ferric phosphate lithium cell making.
Embodiment 1
In the present embodiment, first by anhydrous iron phosphate 40Kg, binding agent PVDF10Kg, conductive agent 5Kg, solvent NMP45Kg is mixed into uniform slurry.In collector aluminium foil strip, be coated with coating machine.Coated anode pole piece 3 is dried.The pending anode pole piece of making 3, continuously by electrochemical processing cell 5, is filled to the lithium nitrate solution of 5% percentage by weight in electrochemical processing cell 5.The voltage of first group of battery lead plate 1 is 1.0V, and the voltage of second group of battery lead plate 2 is 1.7V.Measure at any time the interior lithium ion content of electrochemical processing cell 5, pass into lithium hydroxide solution, ensure the interior lithium ion (Li of electrochemical processing cell 5
+) content and hydroxyl (OH
-) content stable, to maintain carrying out smoothly of 5 reactions in electrochemical processing cell.The electrochemical treatments time is 30 hours.After electrolytic tank electrolysis process, then through twice washed with de-ionized water, after oven dry, compacting, can be made into positive pole piece of lithium iron phosphate battery.
Embodiment 2
In the present embodiment, first by anhydrous iron phosphate 30Kg, binding agent PVDF1Kg, conductive agent 10Kg, solvent NMP59Kg is mixed into uniform slurry.In collector aluminium foil strip, be coated with coating machine.Coated anode pole piece 3 is dried.The pending anode pole piece of making 3, continuously by electrochemical processing cell 5, is filled to the lithium nitrate solution of 25% percentage by weight in electrochemical processing cell 5.The voltage of first group of battery lead plate 1 is 1.2V, and the voltage of second group of battery lead plate 2 is that 2.0V(pole piece is negative pole).Measure at any time the interior lithium ion content of electrochemical processing cell 5, pass into lithium hydroxide solution, ensure the interior lithium ion (Li of electrochemical processing cell 5
+) content and hydroxyl (OH
-) content stable, to maintain carrying out smoothly of electrochemical processing cell 5 interior reactions.The electrochemical treatments time is 10 hours.After electrolytic tank electrolysis process, then through twice washed with de-ionized water, after oven dry, compacting, can be made into positive plate of iron phosphate lithium battery.
Embodiment 3
In the present embodiment, first by anhydrous iron phosphate 50Kg, binding agent PVDF10Kg, conductive agent 1Kg, solvent NMP39Kg is mixed into uniform slurry.In collector aluminium foil strip, be coated with coating machine.Coated anode pole piece 3 is dried.The pending anode pole piece of making 3, continuously by electrochemical processing cell 5, is filled to the lithium nitrate solution of 15% percentage by weight in electrochemical processing cell 5.The voltage of first group of battery lead plate 1 is 1.1V, and the voltage of second group of battery lead plate 2 is that 1.8V(pole piece is negative pole).Measure at any time the interior lithium ion content of electrochemical processing cell 5, pass into lithium hydroxide solution, ensure the interior lithium ion (Li of electrochemical processing cell 5
+) content and hydroxyl (OH
-) content stable, to maintain carrying out smoothly of electrochemical processing cell 5 interior reactions.The electrochemical treatments time is 15 hours.After electrolytic tank electrolysis process, then through twice washed with de-ionized water, after oven dry, compacting, can be made into positive plate of iron phosphate lithium battery.
Above execution mode is only for illustrating the present invention; and be not limitation of the present invention; the those of ordinary skill in relevant technologies field; without departing from the spirit and scope of the present invention; can also make a variety of changes and modification; therefore all technical schemes that are equal to also belong to category of the present invention, and scope of patent protection of the present invention should be defined by the claims.
Claims (8)
1. a cell positive pole piece making method, is characterized in that, comprises the following steps:
S1: anhydrous iron phosphate is mixed to making beating with binding agent, conductive agent and solvent, make stable slurry, coating in aluminium foil strip, oven dry, make anode pole piece;
S2: the anode pole piece in S1 is carried out to electrochemical treatments, and electrochemical treatments solution contains lithium nitrate and lithium hydroxide;
S3: by carrying out washed with de-ionized water, oven dry, compacting containing the anode pole piece of lithium nitrate and lithium hydroxide in S2, make iron phosphate lithium positive pole pole piece.
2. manufacture method as claimed in claim 1, is characterized in that, in S1, the percentage by weight of anhydrous iron phosphate is: 30%～50%; Binding agent is Kynoar, and its percentage by weight is: 1%～10%; The percentage by weight of conductive agent is: 1%～10%; Solvent is 1-METHYLPYRROLIDONE, and its percentage by weight is: 30%～68%.
3. manufacture method as claimed in claim 2, is characterized in that, described conductive agent is one or more in super carbon black, conductive carbon black, carbon fiber or carbon nano-tube.
4. manufacture method as claimed in claim 1, is characterized in that, in S2, in electrochemical treatments solution, the percentage by weight of lithium nitrate is 5%～25%.
5. manufacture method as claimed in claim 1, is characterized in that, in S2, in electrochemical treatments solution, hydroxyl is identical with the content that lithium ion consumes ion.
6. manufacture method as claimed in claim 1, is characterized in that, in S2, the time that described anode pole piece carries out electrochemical treatments is 10～30 hours.
7. manufacture method as claimed in claim 1, it is characterized in that, carry out in electrochemical processing cell in the electrochemical treatments described in S2, first group of battery lead plate and second group of battery lead plate are set in described electrochemical processing cell, every group of upper and lower corresponding setting of battery lead plate, the relative pole piece voltage of described first group of battery lead plate is-1.0V～-1.2V that the relative pole piece voltage of described second group of battery lead plate is-1.7V～-2V; Described electrode slice is first through first group of battery lead plate, then through second group of battery lead plate.
8. manufacture method as claimed in claim 1, is characterized in that, S2 also comprises: in described electrochemical processing cell, pass into electric current 10～20 hours, current density is all to change the ferric phosphate on described anode pole piece into LiFePO4 as standard.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210343207.XA CN102881865B (en) | 2012-09-14 | 2012-09-14 | Method for manufacturing positive plate of battery |
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|---|---|---|---|
| CN201210343207.XA CN102881865B (en) | 2012-09-14 | 2012-09-14 | Method for manufacturing positive plate of battery |
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| CN102881865A CN102881865A (en) | 2013-01-16 |
| CN102881865B true CN102881865B (en) | 2014-09-10 |
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| CN103276406B (en) * | 2013-03-29 | 2017-04-12 | 江西省电力科学研究院 | Electrochemical lithium recovery method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101241987A (en) * | 2008-01-04 | 2008-08-13 | 深圳大学 | An electric chemical compound method for positive material ferric lithium phosphate of lithium ion battery |
| CN101325254A (en) * | 2008-07-15 | 2008-12-17 | 长沙杉杉动力电池有限公司 | Method for manufacturing positive plate of iron phosphate lithium battery |
| CN102610797A (en) * | 2011-12-16 | 2012-07-25 | 北京联飞翔科技股份有限公司 | Manufacturing method of lithium iron phosphate anode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6528033B1 (en) * | 2000-01-18 | 2003-03-04 | Valence Technology, Inc. | Method of making lithium-containing materials |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101241987A (en) * | 2008-01-04 | 2008-08-13 | 深圳大学 | An electric chemical compound method for positive material ferric lithium phosphate of lithium ion battery |
| CN101325254A (en) * | 2008-07-15 | 2008-12-17 | 长沙杉杉动力电池有限公司 | Method for manufacturing positive plate of iron phosphate lithium battery |
| CN102610797A (en) * | 2011-12-16 | 2012-07-25 | 北京联飞翔科技股份有限公司 | Manufacturing method of lithium iron phosphate anode |
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Effective date of registration: 20161205 Address after: 313100 Zhejiang city of Huzhou province Changxing County small town Lang Shan Industrial Park Patentee after: Zhejiang lithium Amperex Technology Limited Address before: 100011 Beijing Dongcheng District Andingmen Street No. 136 block 507 imperial international A Patentee before: Beijing Dingneng Kaiyuan Battery Technology Co., Ltd. |
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