CN102306783A - Multi-layer graphene/lithium iron phosphate intercalated composite material, preparation method thereof, and lithium ion battery adopting multi-layer grapheme/lithium iron phosphate intercalated composite material as anode material - Google Patents
Multi-layer graphene/lithium iron phosphate intercalated composite material, preparation method thereof, and lithium ion battery adopting multi-layer grapheme/lithium iron phosphate intercalated composite material as anode material Download PDFInfo
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- CN102306783A CN102306783A CN201110271677A CN201110271677A CN102306783A CN 102306783 A CN102306783 A CN 102306783A CN 201110271677 A CN201110271677 A CN 201110271677A CN 201110271677 A CN201110271677 A CN 201110271677A CN 102306783 A CN102306783 A CN 102306783A
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Abstract
The invention relates to a lithium iron phosphate intercalated composite material, a preparation method thereof and a lithium ion battery adopting the multi-layer graphene/lithium iron phosphate intercalated composite material as an anode material. In the prior art, the electronic conductivity of the lithium iron phosphate material is poor, high-rate charging/discharging capacity of the lithium ion battery adopting the lithium iron phosphate material as the anode material is poor. The purpose of the present invention is to solve the problems in the prior art, and improve the rapid charging capacity of the power lithium ion battery so as to meet the requirements of the pure electrocar. The composite material is prepared through the following steps that: a rheological phase reaction method is adopted for multi-layer graphene, a trivalent iron salt, a phosphorus compound, a lithium compound and carbon source of small organic molecule to obtain a composite precursor, then the precursor is sintered to obtain the multi-layer graphene/lithium iron phosphate intercalated composite material. The anode slurry of the lithium ion battery anode plate comprises the composite material, a conductive agent and polyvinylidene difluoride. The composite material is an intercalated structure, wherein the lithium iron phosphate particles are intercalated between the multi-layer graphene to form the intercalated structure. The trivalent iron salt is adopted as the raw material, such that the cost is reduced. The lithium ion battery has good charging/discharging cycle performance, wherein the specific capacity is more than 60 mA.h.g<-1> at the rate of 20C.
Description
Technical field
The present invention relates to a kind of composite ferric lithium phosphate material, preparation method and be the lithium ion battery of positive electrode with it.
Background technology
It is good that ferric phosphate lithium cell has a fail safe, has extended cycle life, and advantages of environment protection is the ideal source system that drives electric automobile.But present ferric phosphate lithium cell also is difficult to satisfy pure electric vehicle and plug-in hybrid electric vehicle to the requirement of quickly charging battery aspect high rate capability, restricted the development of ev industry.
The rare good conductivity of graphite; Specific area is big; Has outstanding super capacitor character; If can utilize the rare nanometer laminated structure of multilayer graphite; LiFePO 4 material is compound to the rare interlayer of multilayer graphite; Prepare multi-layer graphene/LiFePO4 intercalation composite material and as the hybrid energy-storing battery of positive electrode; The super capacitor character that graphite is rare when the battery fast charging and discharging can be shared electric current; Make the hybrid energy-storing battery not only have high-energy-density but also have high power density, can satisfy the requirement of pure electric vehicle and plug-in hybrid electric vehicle quickly charging battery.
Summary of the invention
The objective of the invention is in order to solve existing LiFePO 4 material poorly conductive; With it is the problem of the lithium ion battery high rate charge-discharge poor performance of positive electrode, the invention provides a kind of multi-layer graphene/LiFePO4 intercalation composite material, its preparation method and is the lithium ion battery of positive electrode with it.
Multi-layer graphene of the present invention/LiFePO4 intercalation composite material; Be through with multi-layer graphene; Trivalent iron salt; P source compound; Li source compound and organic molecule carbon source adopt rheology mutually legal system get composite precursor; Again the composite precursor sintering is obtained; Wherein, Fe in the trivalent iron salt and the mol ratio of the P in the P source compound are 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1; The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.4～0.8: 1, and the mass ratio of multi-layer graphene and LiFePO4 theoretical yield is 0.005～0.3: 1.
The preparation method of multi-layer graphene of the present invention/LiFePO4 intercalation composite material; Realize through following steps: one, the mol ratio in Fe, P and Li is Fe: P: Li=1: 1: 1～11 ratio takes by weighing trivalent iron salt, P source compound and Li source compound; In the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is that 0.4～0.8: 1 ratio takes by weighing the organic molecule carbon source, is that 0.005～0.3: 1 ratio takes by weighing multi-layer graphene in the mass ratio of multi-layer graphene and LiFePO4 theoretical yield; Two, the trivalent iron salt that step 1 is taken by weighing, P source compound, Li source compound, organic molecule carbon source and multi-layer graphene mix mixture; In mixture, add deionized water then; Ultrasonic stirring obtained dispersion liquid in 2～4 hours again; Wherein, the deionized water quality is 5～10 times of mixture quality; Three, the dispersion liquid that step 2 is obtained places and stirs the rheological body that makes generation under 50～100 ℃ the temperature and be immersed in the rare interlayer of multilayer graphite and form intercalated compound, then intercalated compound is dried to constant weight and makes composite precursor; Four, the composite precursor that step 3 is obtained grind powder, then powder is placed the special atmosphere oven predecomposition of inert gas and/or reducibility gas to get intermediate product, control predecomposition temperature is 200～300 ℃, the predecomposition time is 2～4 hours; Five, the intermediate product that step 4 is obtained places the special atmosphere oven of inert gas and/or reducibility gas to calcine, and is cooled to room temperature then and obtains calcined product, and wherein, calcining heat is 550～650 ℃, and calcination time is 5～12 hours; Six, the calcined product of step 5 is pulverized sorting, promptly get multi-layer graphene/LiFePO4 intercalation composite material.
Rheological body described in the step 3 of the present invention is meant under the effect of stress, produces the object that flows with distortion.The rheological body that forms in this execution mode requires to have solids and is evenly distributed with liquid substance, contacts closely, the characteristics that heat exchange is good.
The present invention is the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material; Comprise positive plate; Negative plate; Barrier film and aluminum-plastic composite membrane; Said barrier film is between positive plate and negative plate; Aluminum-plastic composite membrane is wrapped in positive plate; The periphery of negative plate and barrier film; Wherein, Positive plate is formed by plus plate current-collecting body and anode sizing agent manufacturing; Said anode sizing agent is by mass percentage by multi-layer graphene/LiFePO4 intercalation composite material of 80%～95%; 2%～10% conductive agent and 3%～10% binding agent Kynoar are formed, and the coated face density of anode sizing agent in the anode collection surface is 50～200g/m
2
The interlayer that is interspersed in multi-layer graphene for the LiFePO4 of minimum particle diameter (being lower than 10nm) in multi-layer graphene of the present invention/LiFePO4 intercalation composite material forms sandwich.This special construction is mainly reflected in the positive role of material property: 1. the multi-layer graphene specific area is very big and conductivity is good; Add the conductive network that just can in material, form 3 D stereo on a small quantity; Increased the electron conduction of material; Simultaneously; Make the surface area of electrochemical reaction increase greatly; Thereby significantly reduced the interface current density in the electrochemical reaction process, reduced the electrochemical reaction polarization; 2. the multi-layer graphene that is adopted is the dough with layer structure, interlamellar spacing big (about 7～8nm), can form small LiFePO4 particle at interlayer, the ions diffusion approach has been shortened in the growth of limiting material particle diameter, reduces the ions diffusion resistance; 3. the LiFePO4 that does not get into interlayer may have grown into larger particles (about 100nm), and the particle outside is surrounded by carbon-coating, has restricted the further growth of particle, has improved the electron conduction of material monolithic.4. the bigger serface of multi-layer graphene can make it in the extremely short time, realize the storage and the release of a large amount of electric charges, has super capacitor character.With multi-layer graphene/LiFePO4 intercalation composite material be the lithium ion battery of positive electrode when carrying out high rate charge-discharge, the multi-layer graphene material very first time is realized capability response, thereby has guaranteed the high rate performance that lithium ion battery is superior.
The preparation method of multi-layer graphene of the present invention/LiFePO4 intercalation composite material uses than is easier to the trivalent iron salt for preparing and store as reaction raw materials, compares as raw material with adopting ferrous salt, and cost reduces; (the C number is 5～15 organic carbon source to adopt the organic molecule carbon source; Like sucrose, glucose) raw material; It has three effects in trivalent iron salt is the course of reaction of raw material: 1. the micromolecule carbon source is decomposed the carbon that produces and can be used as ferric reducing agent, makes it be reduced to divalence (iron in the LiFePO4 is divalence); 2. decompose the surface that the carbon that produces can be coated on the LiFePO4 particle, become particle and intergranular space obstacle, limited the size of particle, suppress its undue growth; 3. the carbon-coating of LiFePO4 particle surface has good electron conductivity, improves the conductivity of material to a certain extent, and then has improved the high rate performance of lithium ion battery.The preparation method adopts rheology phase method to prepare composite ferric lithium phosphate material simultaneously; Rheology phase method has sol-gal process concurrently, and (raw materials mix is even, full contact; The preparation sample particle is little and even; But complex process, cycle are long) (technology is simple but sample particle that prepare is bigger with carbothermic method; Calcining heat is higher; Time is longer) advantage, can be under relatively low temperature and short time in prepare that particle is less, the material of even size distribution.
With multi-layer graphene of the present invention/LiFePO4 intercalation composite material is the lithium ion battery of positive electrode; Have following performance: the high rate charge-discharge cycle performance that (1) is good: under the 10C charge-discharge magnification, the capability retention of 70 circulation back lithium ion batteries still is higher than 95%; (2) discharge specific discharge capacity: 1C discharge＞140mAhg
-1, 5C discharge＞120mAhg
-1, 10C discharge＞110mAhg
-1, 20C discharge＞100mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode; (3) rapid charge characteristic: earlier with the 1C constant-current discharge to 2.5V; Again with the 20C constant current charge to 4.2V; Constant voltage charge then, can be charged in 200 seconds 95%, 400 second of total capacity can be charged to total capacity 98% (the charging specific discharge capacity of positive active material under this system is 150mAhg
-1).
Description of drawings
Fig. 1 be embodiment ten the charging and discharging curve of lithium ion battery under the 0.2C charge-discharge magnification, curve 1 is a charging curve, curve 2 is discharge curves; Fig. 2 is the high rate performance curve of the lithium ion battery of embodiment ten; Fig. 3 is the cycle performance curve of lithium ion battery under the 10C charge-discharge magnification of embodiment ten; Fig. 4 be embodiment ten lithium ion battery formerly with the 1C constant-current discharge to 2.5V, again with the 20C constant current charge to 4.2V, the rapid charge characteristic curve in the charge and discharge mode of constant voltage charge then.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: this execution mode is multi-layer graphene/LiFePO4 intercalation composite material; It is through with multi-layer graphene; Trivalent iron salt; P source compound; Li source compound and organic molecule carbon source adopt rheology mutually legal system get composite precursor; Again the composite precursor sintering is obtained; Wherein, Fe in the trivalent iron salt and the mol ratio of the P in the P source compound are 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1; The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.4～0.8: 1, and the mass ratio of multi-layer graphene and LiFePO4 theoretical yield is 0.005～0.3: 1.
The sandwich of multi-layer graphene in this execution mode/LiFePO4 intercalation composite material is mainly reflected in the positive role that material property promotes: 1. the multi-layer graphene specific area is very big and conductivity is good; Add the conductive network that just can in material, form 3 D stereo on a small quantity; Increased the electron conduction of material; Simultaneously; Make the surface area of electrochemical reaction increase greatly; Thereby significantly reduced the interface current density in the electrochemical reaction process, reduced the electrochemical reaction polarization; 2. the multi-layer graphene that is adopted is the dough with layer structure, interlamellar spacing big (about 7～8nm), can form small LiFePO4 particle at interlayer, the ions diffusion approach has been shortened in the growth of limiting material particle diameter, reduces the ions diffusion resistance; 3. the LiFePO4 that does not get into interlayer may have grown into larger particles (about 100nm), and the particle outside is surrounded by carbon-coating, has restricted the further growth of particle, has improved the electron conduction of material monolithic.4. the bigger serface of multi-layer graphene can make it in the extremely short time, realize the storage and the release of a large amount of electric charges.With multi-layer graphene/LiFePO4 intercalation composite material be the lithium ion battery of positive electrode when carrying out high rate charge-discharge, the multi-layer graphene material very first time is realized capability response, thereby has guaranteed the high rate performance that lithium ion battery is superior.
Multi-layer graphene/LiFePO4 intercalation composite material with this execution mode is the lithium ion battery of positive electrode; Have following performance: the high rate charge-discharge cycle performance that (1) is good: under the 10C charge-discharge magnification, the capability retention of 70 circulation back lithium ion batteries still is higher than 95%; (2) discharge specific discharge capacity: 1C discharge＞140mAhg
-1, 5C discharge＞120mAhg
-1, 10C discharge＞110mAhg
-1, 20C discharge＞100mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode; (3) rapid charge characteristic: earlier with the 1C constant-current discharge to 2.5V; Again with the 20C constant current charge to 4.2V; Constant voltage charge then, can be charged in 200 seconds 95%, 400 second of total capacity can be charged to total capacity 98% (the charging specific discharge capacity of positive active material under this system is 150mAhg
-1).
Embodiment two: what this execution mode and embodiment one were different is that said trivalent iron salt is ferric nitrate or iron chloride; Said P source compound is ammonium dihydrogen phosphate or ammonium hydrogen phosphate; Said Li source compound is a kind of or wherein several mixture in lithium nitrate, lithium carbonate and the lithium hydroxide, and said organic molecule carbon source is sucrose and/or glucose.Other parameter is identical with embodiment one.
When Li source compound is mixture, mix in this execution mode with any ratio.When organic micromolecule carbon source is two kinds mixture, with sucrose C
12H
22O
11With glucose C
6H
12O
6Mol ratio be 1: 2～4 mixed.
Embodiment three: this execution mode is different with embodiment one or two is that the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.5～0.7: 1.Other parameter is identical with embodiment one or two.
What the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield was best in this execution mode is 0.6: 1.
Embodiment four: this execution mode and embodiment one, two or three are different is that the mass ratio of multi-layer graphene and LiFePO4 theoretical yield is 0.008～0.2: 1.Other parameter is identical with embodiment one, two or three.
The mass ratio of multi-layer graphene and LiFePO4 theoretical yield is preferably 0.01～0.1 in this execution mode, optimally is 0.05: 1.
Embodiment five: this execution mode is the preparation method of multi-layer graphene/LiFePO4 intercalation composite material; It is realized through following steps: one, the mol ratio in Fe, P and Li is Fe: P: Li=1: 1: 1～1.1 ratio takes by weighing trivalent iron salt, P source compound and Li source compound; In the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is that 0.4～0.8: 1 ratio takes by weighing the organic molecule carbon source, is that 0.005～0.3: 1 ratio takes by weighing multi-layer graphene in the mass ratio of multi-layer graphene and LiFePO4 theoretical yield; Two, the trivalent iron salt that step 1 is taken by weighing, P source compound, Li source compound, organic molecule carbon source and multi-layer graphene mix mixture; In mixture, add deionized water then; Ultrasonic stirring obtained dispersion liquid in 2～4 hours again; Wherein, the deionized water quality is 5～10 times of mixture quality; Three, the dispersion liquid that step 2 is obtained places and stirs the rheological body that makes generation under 50～100 ℃ the temperature and be immersed in the rare interlayer of multilayer graphite and form intercalated compound, then intercalated compound is dried to constant weight and makes composite precursor; Four, the composite precursor that step 3 is obtained grind powder, then powder is placed the special atmosphere oven predecomposition of inert gas and/or reducibility gas to get intermediate product, control predecomposition temperature is 200～300 ℃, the predecomposition time is 2～4 hours; Five, the intermediate product that step 4 is obtained places the special atmosphere oven of inert gas and/or reducibility gas to calcine, and is cooled to room temperature then and obtains calcined product, and wherein, calcining heat is 550～650 ℃, and calcination time is 5～12 hours; Six, the calcined product of step 5 is pulverized sorting, promptly get multi-layer graphene/LiFePO4 intercalation composite material.
The multi-layer graphene that this execution mode obtains/LiFePO4 intercalation composite material is the interlayer formation sandwich that the LiFePO4 of minimum particle diameter (being lower than 10nm) is interspersed in multi-layer graphene.Adopt than the trivalent iron salt that is easier to prepare and stores as reaction raw materials, it is compared as raw material with the use ferrous salt, and cost is lower.
Rheology in this execution mode step 2 and step 3 method mutually is a kind of new method of synthesizing inorganic nonmetallic materials; This method is after solid reactant is mixed according to a certain percentage; Be dissolved in an amount of water or other solvents and form true solution; Mode through heating or stirring makes liquid viscosity increase then; The rheological body that formation solids and liquid substance are evenly distributed (is that rheological body described in the step 3 is meant under the effect of stress, produces the object that flows with distortion.The rheological body that forms in this execution mode requires to have solids and is evenly distributed with liquid substance, contacts closely, the characteristics that heat exchange is good).In rheological body, the surface energy of solia particle is utilized effectively, and solids contact with liquid substance closely, evenly, and heat exchange is good, is not easy to occur the local overheating phenomenon.Compare with high temperature solid-state synthesis method commonly used, this method has advantages such as synthesis temperature is low, and roasting time is short, and the gained material granule is little and be evenly distributed.
The multi-layer graphene specific area that adopts in this execution mode is very big and conductivity is good; Add the conductive network that just can in material, form 3 D stereo on a small quantity; Increased the electron conduction of material; Make the surface area of electrochemical reaction increase greatly; Thereby significantly reduced the interface current density in the electrochemical reaction process, reduced the electrochemical reaction polarization; Interlamellar spacing big (about 7～8nm), can form small LiFePO4 particle at interlayer, the ions diffusion approach has been shortened in the growth of limiting material particle diameter, reduces the ions diffusion resistance; Its bigger specific area can realize the storage and the release of a large amount of electric charges in the extremely short time.The objective of the invention is to by adopting the adding of rheology phase method synthesis technique and multi-layer graphene; Make the multi-layer graphene/LiFePO4 intercalation composite material that obtains possess special intercalation configuration; And the large current density electrical feature that possesses electric chemical super capacitor; Thereby the lithium ion battery that this Composite Preparation of application is gone out not only can utilize the characteristic of multi-layer graphene material fast charging and discharging; Increase the electrochemical reaction surface area of LiFePO 4 material simultaneously and shortened lithium ion diffusion path; Reduced the interfacial reaction polarization of this material in charge and discharge process, the comprehensive function of the two has significantly improved the high rate charge-discharge performance of lithium ion battery.
The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield preferably is 0.5～0.7: 1 in this execution mode step 1, and best is 0.6: 1.
The mass ratio of multi-layer graphene and LiFePO4 theoretical yield preferably is 0.005～0.3: 1 in the step 1, is 0.008～0.2 better, more preferably is 0.01～0.1, optimally is 0.05: 1.
Be that-0.5 MPa, temperature are to be dried to constant weight under 110 ℃ the condition to make composite precursor with intercalated compound in vacuum degree in the step 3.
In the step 4 more preferably be, control predecomposition temperature is 260 ℃, and the predecomposition time is 2 hours.
In the step 5 more preferably be, calcining heat is 600 ℃, and calcination time is 10 hours.
In the step 6, carry out sorting after adopting 400 mesh sieves that the calcined product of step 5 is pulverized.
Embodiment six: what this execution mode and embodiment five were different is that trivalent iron salt described in the step 1 is ferric nitrate or iron chloride; Said P source compound is ammonium dihydrogen phosphate or ammonium hydrogen phosphate; Said Li source compound is a kind of or wherein several mixture in lithium nitrate, lithium carbonate and the lithium hydroxide, and said organic molecule carbon source is sucrose and/or glucose.Other parameter is identical with embodiment five.
When Li source compound is mixture, mix in this execution mode with any ratio.When organic micromolecule carbon source is two kinds mixture, with sucrose C
12H
22O
11With glucose C
6H
12O
6Mol ratio be 1: 2～4 mixed.
Embodiment seven: this execution mode is the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material; Comprise positive plate; Negative plate; Barrier film and aluminum-plastic composite membrane; Said barrier film is between positive plate and negative plate; Aluminum-plastic composite membrane is wrapped in positive plate; The periphery of negative plate and barrier film; Wherein, Positive plate is formed by plus plate current-collecting body and anode sizing agent manufacturing; Said anode sizing agent is by mass percentage by multi-layer graphene/LiFePO4 intercalation composite material of 80%～95%; 2%～10% conductive agent and 3%～10% binding agent Kynoar are formed, and the coated face density of anode sizing agent in the anode collection surface is 50～200g/m
2
This execution mode be the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material; Have following performance: the high rate charge-discharge cycle performance that (1) is good: under the 10C charge-discharge magnification, the capability retention of 70 circulation back lithium ion batteries still is higher than 95%; (2) discharge specific discharge capacity: 1C discharge＞140mAhg
-1, 5C discharge＞120mAhg
-1, 10C discharge＞110mAhg
-1, 20C discharge＞100mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode; (3) rapid charge characteristic: earlier with the 1C constant-current discharge to 2.5V; Again with the 20C constant current charge to 4.2V; Constant voltage charge then, can be charged in 200 seconds 95%, 400 second of total capacity can be charged to total capacity 98% (the charging specific discharge capacity of positive active material under this system is 150mAhg
-1).
Anode sizing agent is single face coating in the anode collection surface in this execution mode, anode sizing agent the coated face density of anode collection surface preferable be 80～150g/m
2, that more excellent is 100g/m
2
And when anode sizing agent evenly was coated in the upper and lower surface of plus plate current-collecting body, the twice the when surface density of anode sizing agent is the single face coating was 100～400g/m
2
Plus plate current-collecting body in this execution mode is an aluminium foil.
Negative plate described in this execution mode is formed by negative current collector and cathode size manufacturing, adopts and well known to a person skilled in the art that negative plate gets final product.For example, cathode size can be by mass percentage be made up of the binding agent Kynoar of the active carbon of 75%～97% graphite type material, 0～15% high-specific surface area and 3%～10% and (be preferably in the cathode size by mass percentage by the active carbon of 80%～90% graphite type material, 5%～12% high-specific surface area and 4%～8% binding agent Kynoar and forms.More preferably be to form by the active carbon of 85% graphite type material, 9% high-specific surface area and 6% binding agent Kynoar by mass percentage), cathode size is evenly distributed on the one side of negative current collector, and the surface density of cathode size is 20～100g/m
2Wherein said graphite type material can be for one or more the mixture in native graphite, Delanium and the carbonaceous mesophase spherules, when graphite type material is mixture, with any than mixing; Said negative current collector can be Copper Foil.When cathode size evenly was coated in the upper and lower surface of plus plate current-collecting body, the twice the when surface density of cathode size is the single face coating was 40～200g/m
2
Embodiment eight: what this execution mode and embodiment seven were different is that said conductive agent is a kind of or wherein several mixture in nano-graphite, acetylene black and the carbon black.Other parameter is identical with embodiment seven.
When conductive agent is mixture, mix in this execution mode with any ratio.
Embodiment nine: this execution mode is different with embodiment seven or eight is that said anode sizing agent is made up of multi-layer graphene/LiFePO4 intercalation composite material of 80%～90%, 5%～10% conductive agent and 5%～10% binding agent Kynoar by mass percentage.Other parameter is identical with embodiment seven or eight.
Embodiment ten: this execution mode is different with embodiment seven or eight is that said anode sizing agent is made up of multi-layer graphene/LiFePO4 intercalation composite material of 80%, 10% conductive agent and 10% binding agent Kynoar by mass percentage, and the coated face density of anode sizing agent in the anode collection surface is 100g/m
2Other parameter is identical with embodiment seven or eight.
Conductive agent described in this execution mode is a nano-graphite.
Multi-layer graphene described in this execution mode/LiFePO4 intercalation composite material; Realize through following steps: one, the mol ratio in Fe, P and Li is Fe: P: Li=1: 1: 1.05 ratio takes by weighing ferric nitrate, ammonium dihydrogen phosphate and lithium nitrate; In the mass ratio of sucrose and LiFePO4 theoretical yield is that 0.6: 1 ratio takes by weighing sucrose, is that 0.05: 1 ratio takes by weighing multi-layer graphene in the mass ratio of multi-layer graphene and LiFePO4 theoretical yield; Two, the ferric nitrate that step 1 is taken by weighing, ammonium dihydrogen phosphate, lithium nitrate, sucrose and multi-layer graphene mix mixture; In mixture, add deionized water then; Obtained dispersion liquid in 2 hours 40 ℃ of following ultrasonic stirring again, wherein, the deionized water quality is 5 times of mixture quality; Three, the dispersion liquid that step 2 is obtained places and stirs the rheological body that makes generation under 80 ℃ the temperature and be immersed in the rare interlayer of multilayer graphite and form intercalated compound; Be-0.5 MPa with intercalated compound in vacuum degree then, baking temperature is to be dried to constant weight under 110 ℃ the condition to make composite precursor; Four, the composite precursor that step 3 is obtained grinds 5min and gets powder, then powder is placed the tube furnace predecomposition of the protective atmosphere of inert gas to get intermediate product, and control predecomposition temperature is 260 ℃, and the predecomposition time is 2 hours; Five, the intermediate product that step 4 is obtained places the tube furnace of the protective atmosphere of inert gas to calcine, and is cooled to room temperature then and obtains calcined product, and wherein, calcining heat is 600 ℃, and calcination time is 10 hours; Six, after the calcined product pulverizing with step 5, cross 400 mesh sieves and carry out sorting, promptly get multi-layer graphene/LiFePO4 intercalation composite material.Wherein, multi-layer graphene is the commercially available prod.
The cathode size of this execution mode is made up of the active carbon of 85% graphite type material, 9% high-specific surface area and 6% binding agent Kynoar by mass percentage; Cathode size is evenly distributed on the one side of negative current collector, and the surface density of cathode size is 60g/m
2Wherein said graphite type material is a native graphite; Said negative current collector can be Copper Foil.
This execution mode be that the lithium ion battery of positive electrode prepares through following steps with multi-layer graphene/LiFePO4 intercalation composite material: one, take by weighing following anode sizing agent raw material by mass percentage: 80% multi-layer graphene/LiFePO4 intercalation composite material, 10% acetylene black conductive agent and 10% binding agent Kynoar (PVDF) are formed, and then take by weighing following cathode size raw material by mass percentage: the active carbon of 85% graphite type material, 9% high-specific surface area and 6% binding agent Kynoar; Two, anodal raw material that step 1 is taken by weighing and negative pole raw material are that-0.5～-0.1 MPa, temperature are under 100～120 ℃ the condition in vacuum degree respectively, vacuumize 6 hours; Three, with the anode sizing agent raw materials mix after the step 2 processing; Adding dispersant n-formyl sarcolysine base pyrrolidones (NMP) again stirred 6～8 hours; Get anode sizing agent; NMP is 3 times of anode sizing agent raw material binding agent PVDF quality, and then will the cathode size raw materials mix after step 2 is handled stirs and promptly get cathode size; Four, anode sizing agent evenly is coated on the plus plate current-collecting body, it is 100gm that control applies single face density
-2(perhaps two-sided density is 200gm
-2), obtain wet positive plate, again cathode size evenly is coated on the negative current collector, it is 60gm that control applies single face density
-2(perhaps two-sided density is 120gm
-2), obtain wet negative plate; Five, wet positive plate that step 4 is obtained and wet negative plate drying in vacuum drying chamber obtained positive plate and negative plate in 4 hours, and wherein drying condition is: vacuum degree-0.5～-0.1 MPa, 100～120 ℃ of baking temperatures.Six, step 5 is obtained positive plate and negative plate, barrier film and aluminum-plastic composite membrane assemble soft-package battery; Wherein being infused in the argon gas glove box of electrolyte for lithium ion battery carried out, and promptly accomplishing multi-layer graphene/LiFePO4 intercalation composite material is the preparation method of the lithium ion battery of positive electrode.
As a comparison; Carry out following contrast experiment: lithium ion battery; Comprise positive plate, negative plate, barrier film and aluminum-plastic composite membrane; Said barrier film is between positive plate and negative plate; Aluminum-plastic composite membrane is wrapped in the periphery of positive plate, negative plate and barrier film; Wherein, Positive plate is formed by plus plate current-collecting body aluminium foil and anode sizing agent manufacturing; Said anode sizing agent is made up of 80% LiFePO4,10% acetylene black conductive agent and 10% binding agent Kynoar by mass percentage, and the coated face density of anode sizing agent in the anode collection surface is 100g/m
2Wherein, LiFePO4 is existing commercially available prod.Negative plate is the same with negative plate in the embodiment ten.Its preparation method be that the preparation method of lithium ion battery of positive electrode is consistent with multi-layer graphene/LiFePO4 intercalation composite material described in the embodiment ten, different is to adopt LiFePO4 to replace multi-layer graphene/LiFePO4 intercalation composite material.
The lithium ion battery that lithium ion battery that embodiment ten is obtained and contrast experiment obtain; Carry out battery performance test respectively; Method of testing is: charging-discharge tester system is the BTS series high accuracy battery test macro that Shenzhen new Weir company produces; Experimental cell is 2025 button cells; The charging cut-ff voltage is 4.2V; Discharge cut-off voltage is 2.5V; The battery charging and discharging system is that first constant current charge is to the cut-ff voltage that charges; Constant voltage charge a period of time again; Battery discharge is to discharge cut-off voltage after leaving standstill a period of time, a loop ends.
The charging and discharging curve of lithium ion battery under the 0.2C charge-discharge magnification of the embodiment ten that test obtains, as shown in Figure 1, curve 1 is a charging curve among the figure, curve 2 is discharge curves.Visible by Fig. 1, the lithium ion battery of embodiment ten has bigger specific discharge capacity, discharge capacity＞150mAhg under the 0.2C charge-discharge magnification under little multiplying power
-1
The high rate performance curve of the lithium ion battery of the embodiment ten that test obtains, as shown in Figure 2, " C " expression discharge-rate among the figure.Visible by Fig. 2, the lithium ion battery of embodiment ten has superior high rate performance, discharge specific discharge capacity: 1C discharge＞140mAhg
-1, 5C discharge＞120mAhg
-1, 10C discharge＞110mAhg
-1, 20C discharge＞100mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode.
The cycle performance curve of lithium ion battery under the 10C charge-discharge magnification of the embodiment ten that test obtains, as shown in Figure 3.Visible by Fig. 3, the lithium ion battery of embodiment ten has superior cycle performance: the capability retention of 70 circulation back lithium ion batteries still is higher than 95%.
The lithium ion battery of the embodiment ten that obtains of test formerly with the 1C constant-current discharge to 2.5V, again with the 20C constant current charge to 4.2V, the rapid charge characteristic curve in the charge and discharge mode of constant voltage charge then, as shown in Figure 4.Visible by Fig. 4, the lithium ion battery of embodiment ten has the superior performance of filling soon, can be charged in 200 seconds 95%, 400 second of total capacity can be charged to total capacity 98% (the charging specific discharge capacity of positive active material under this system is 150mAhg
-1).
Test the lithium ion battery of embodiment ten and lithium ion battery specific discharge capacity under different discharge-rates of contrast experiment simultaneously, as shown in table 1.
Table 1 is the lithium ion battery of embodiment ten and lithium ion battery specific discharge capacity under different discharge-rates of contrast experiment.Wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode.
Table 1
It is thus clear that the lithium ion battery of concrete mode ten has well big multiplying power specific discharge capacity, the high rate charge-discharge performance is good.The rated voltage of the lithium ion battery that practical implementation ten obtains is 3.2V.
Claims (10)
1. multi-layer graphene/LiFePO4 intercalation composite material; It is characterized in that multi-layer graphene/LiFePO4 intercalation composite material is through with multi-layer graphene; Trivalent iron salt; P source compound; Li source compound and organic molecule carbon source adopt rheology mutually legal system get composite precursor; Again the composite precursor sintering is obtained; Wherein, Fe in the trivalent iron salt and the mol ratio of the P in the P source compound are 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1; The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.4～0.8: 1, and the mass ratio of multi-layer graphene and LiFePO4 theoretical yield is 0.005～0.3: 1.
2. multi-layer graphene according to claim 1/LiFePO4 intercalation composite material; It is characterized in that said trivalent iron salt is ferric nitrate or iron chloride; Said P source compound is ammonium dihydrogen phosphate or ammonium hydrogen phosphate; Said Li source compound is a kind of or wherein several mixture in lithium nitrate, lithium carbonate and the lithium hydroxide, and said organic molecule carbon source is sucrose and/or glucose.
3. multi-layer graphene according to claim 1 and 2/LiFePO4 intercalation composite material, the mass ratio that it is characterized in that organic molecule carbon source and LiFePO4 theoretical yield is 0.5～0.7: 1.
4. multi-layer graphene according to claim 1 and 2/LiFePO4 intercalation composite material, the mass ratio that it is characterized in that multi-layer graphene and LiFePO4 theoretical yield is 0.008～0.2: 1.
5. the preparation method of multi-layer graphene as claimed in claim 1/LiFePO4 intercalation composite material; The preparation method who it is characterized in that multi-layer graphene/LiFePO4 intercalation composite material realizes through following steps: one; Press Fe; The mol ratio of P and Li is Fe: P: Li=1: 1: 1～1.1 ratio takes by weighing trivalent iron salt; P source compound and Li source compound; In the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is that 0.4～0.8: 1 ratio takes by weighing the organic molecule carbon source, is that 0.005～0.3: 1 ratio takes by weighing multi-layer graphene in the mass ratio of multi-layer graphene and LiFePO4 theoretical yield; Two, the trivalent iron salt that step 1 is taken by weighing, P source compound, Li source compound, organic molecule carbon source and multi-layer graphene mix mixture; In mixture, add deionized water then; Ultrasonic stirring obtained dispersion liquid in 2～4 hours again; Wherein, the deionized water quality is 5～10 times of mixture quality; Three, the dispersion liquid that step 2 is obtained places and stirs the rheological body that makes generation under 50～100 ℃ the temperature and be immersed in the rare interlayer of multilayer graphite and form intercalated compound, then intercalated compound is dried to constant weight and makes composite precursor; Four, the composite precursor that step 3 is obtained grind powder, then powder is placed the special atmosphere oven predecomposition of inert gas and/or reducibility gas to get intermediate product, control predecomposition temperature is 200～300 ℃, the predecomposition time is 2～4 hours; Five, the intermediate product that step 4 is obtained places the special atmosphere oven of inert gas and/or reducibility gas to calcine, and is cooled to room temperature then and obtains calcined product, and wherein, calcining heat is 550～650 ℃, and calcination time is 5～12 hours; Six, the calcined product of step 5 is pulverized sorting, promptly get multi-layer graphene/LiFePO4 intercalation composite material.
6. the preparation method of multi-layer graphene according to claim 5/LiFePO4 intercalation composite material; It is characterized in that trivalent iron salt described in the step 1 is ferric nitrate or iron chloride; Said P source compound is ammonium dihydrogen phosphate or ammonium hydrogen phosphate; Said Li source compound is a kind of or wherein several mixture in lithium nitrate, lithium carbonate and the lithium hydroxide, and said organic molecule carbon source is sucrose and/or glucose.
7. be the lithium ion battery of positive electrode with multi-layer graphene as claimed in claim 1/LiFePO4 intercalation composite material; Comprise positive plate; Negative plate; Barrier film and aluminum-plastic composite membrane; Said barrier film is between positive plate and negative plate; Aluminum-plastic composite membrane is wrapped in positive plate; The periphery of negative plate and barrier film; It is characterized in that positive plate is formed by plus plate current-collecting body and anode sizing agent manufacturing; Said anode sizing agent is by mass percentage by multi-layer graphene/LiFePO4 intercalation composite material of 80%～95%; 2%～10% conductive agent and 3%～10% binding agent Kynoar are formed, and the coated face density of anode sizing agent in the anode collection surface is 50～200g/m
2
8. according to claim 7 is the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material, it is characterized in that said conductive agent is a kind of or wherein several mixture in nano-graphite, acetylene black and the carbon black.
According to claim 7 or 8 described be the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material, it is characterized in that said anode sizing agent is made up of multi-layer graphene/LiFePO4 intercalation composite material of 80%～90%, 5%～10% conductive agent and 5%～10% binding agent Kynoar by mass percentage.
According to claim 7 or 8 described be the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material; It is characterized in that said anode sizing agent is made up of multi-layer graphene/LiFePO4 intercalation composite material of 80%, 10% conductive agent and 10% binding agent Kynoar by mass percentage, the coated face density of anode sizing agent in the anode collection surface is 100g/m
2
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Application publication date: 20120104 |