CN103022485A - Lithium manganese phosphate-clad lithium manganate lithium secondary battery anode material and preparation method thereof - Google Patents
Lithium manganese phosphate-clad lithium manganate lithium secondary battery anode material and preparation method thereof Download PDFInfo
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- CN103022485A CN103022485A CN2012105553647A CN201210555364A CN103022485A CN 103022485 A CN103022485 A CN 103022485A CN 2012105553647 A CN2012105553647 A CN 2012105553647A CN 201210555364 A CN201210555364 A CN 201210555364A CN 103022485 A CN103022485 A CN 103022485A
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Abstract
The invention provides a lithium ion secondary battery anode material. The material is expressed by the formula xLiMnPO4/(1-x)LiMn2O4, and a LiMnPO4 film is coated with LiMn2O4, wherein x is not less than 0 and not more than 0.1. The invention further provides a preparation method of the anode material, and a lithium ion secondary battery anode and a lithium ion secondary battery using the anode material. The surface decoration is implemented for the LiMn2O4 material by the cheap and environment-friendly lithium ion battery anode material LiMnPO4 with an olivine structure, so that on one hand, the existence of the film can prevent electrolyte from being decomposed on the surface of an active substance to improve the high temperature characteristic, and on the other hand, the specific capacity of the lithium manganate battery at the high temperature is improved by using the electrochemical activity of the lithium manganese phosphate anode material.
Description
Technical field
The invention belongs to the battery technology field, be specifically related to a kind of lithium ion secondary battery anode material and preparation method thereof, lithium ion secondary battery positive electrode and lithium rechargeable battery.
Background technology
Secondary cell is called again rechargeable battery, is can make active material activate the battery that continues use by the mode of charging behind battery discharge.With respect to dry cell, the cycle charging number of times of secondary cell can reach thousands of to tens thousand of times, is a kind of novel environment-friendly battery.
Secondary cell in the market mainly comprises lead-acid battery, ickel-cadmium cell, Ni-MH battery and lithium ion battery.The comparatively environmental protection but energy density is lower of lead-acid battery low price but contain the heavy metal lead of contaminated environment, ickel-cadmium cell, the Ni-MH battery energy density is higher but have slight memory effect, and efficiency for charge-discharge is poor under the hot environment.With respect to lead-acid battery, ickel-cadmium cell and Ni-MH battery, lithium ion battery has higher specific energy, the discharge curve balance, and self-discharge rate is low, and cycle life is longer, memory-less effect, environmentally safe is the green battery that grew up in the last few years.
Lithium rechargeable battery comprises positive pole, negative pole, is arranged on barrier film and electrolyte between positive pole and the negative pole.Wherein, positive pole comprises matrix and the coating material that is coated on this matrix, and wherein coating material comprises positive electrode (positive active material), electric conducting material and binding agent.Positive electrode is the crucial raw material of lithium rechargeable battery, because positive electrode occupies larger weight ratio in lithium rechargeable battery, so the positive electrode performance has determined build, fail safe and the electric property of battery.
Lithium ion battery is owing to have higher energy density, long cycle life, the plurality of advantages such as lower self-discharge rate and environmental friendliness, it has been present mobile phone, digital camera, the reference power supply of the mobile communication equipments such as notebook computer, simultaneously, at new-energy automobile, also placed high hopes by people in the energy storage aspect of wind power generation and solar power generation.Yet if successfully apply in these areas, lithium ion battery just must be in battery price, fail safe, and further lifting is done in the aspects such as useful life.
The positive electrode that uses in the current lithium ion battery mostly is greatly LiCoO
2, also have part LiNi
1-xCo
xO
2, LiFePO
4And LiMn
2O
4For LiCoO
2, because the abundance of cobalt in the earth's crust be very low, so the price of cobalt is very expensive, and cobalt has certain toxicity, environment is had harmful effect after discarded; LiNi
1-xCo
xO
2With LiCoO
2Compare, use in reality increasing aspect the capacity, price also decreases, but has the problems such as fail safe is relatively poor; LiFePO
4Have Stability Analysis of Structures, raw material is cheap, and cyclicity and fail safe are better, to advantages such as environmental pressure are less, but the problem such as it is higher also to exist synthetic cost, and energy density is lower; Spinelle LiMn
2O
4Have that fail safe is good, multiplying power property is good, price is low, the advantages such as environmental protection, it also is present a kind of main flow positive electrode, but its energy density is on the low side, capacity attenuation in charge and discharge cycles is very fast, particularly at high temperature cycle performance is relatively poor, has limited its application on large-sized power lithium ion battery and energy-storage battery.Cause LiMn
2O
4The relatively poor reason of material at high temperature characteristic and large current characteristic has a lot, such as the dissolving of the manganese under Jahn-Teller distortion effect and the high temperature, electrolyte decomposition etc.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of lithium ion secondary battery anode material, make it have excellent high-temperature stability and the large specific capacity under the high temperature.
For achieving the above object, the invention provides following technical scheme:
Lithium ion secondary battery anode material of the present invention is used general formula xLiMnPO
4/ (1-x) LiMn
2O
4Expression is by LiMnPO
4Film coated LiMn
2O
4, 0≤x≤0.1 wherein.
The present invention also provides a kind of method for preparing above-mentioned lithium ion secondary battery anode material, specifically comprises the steps:
Take by weighing water-soluble Li source compound, water-soluble manganese source compound, ammonium phosphate salt and citric acid according to mol ratio Li:Mn:P: citric acid=3:1:1:1, add distilled water mixing wiring solution-forming, add the LiMn of stoichiometric proportion
2O
4Magnetic agitation 3 ~ 5h, be transferred in the hydro-thermal inner bag of polytetrafluoroethylene, add water to 70 ~ 80vol% of inner bag, put into stainless steel cauldron, place 180 ~ 200 ℃ vacuum drying oven to react 8 ~ 12h, naturally cool to room temperature, after carrying out repeatedly centrifugation and washing, with 100 ~ 120 ℃ of lower dry 10 ~ 12h of products therefrom, grinding namely obtains LiMnPO after taking out
4Coat LiMn
2O
4Positive electrode.
Described water-soluble manganese source compound is selected from manganese acetate, manganese nitrate, manganese chloride or manganese sulfate; Described water-soluble Li source compound is selected from lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate; Described ammonium phosphate salt is ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
Preferably, described water-soluble manganese source compound is manganese acetate; Described water-soluble Li source compound is lithium hydroxide.
Further, the invention provides a kind of lithium ion secondary battery positive electrode, comprise matrix and the coating material that places matrix surface, described coating material comprises: above-mentioned positive electrode, electric conducting material and bonding agent.
Further, the present invention also provides a kind of lithium rechargeable battery, comprising: above-mentioned lithium ion secondary battery positive electrode, negative pole, be arranged on barrier film and electrolyte between positive pole and the negative pole.
The present invention adopts cheapness, environmental protection, has the anode material for lithium-ion batteries LiMnPO of olivine structural
4To LiMn
2O
4Material carries out finishing, and the existence of this film can prevent electrolyte in the decomposition on active material surface on the one hand, and then improves its hot properties; Utilize on the other hand the electro-chemical activity of manganese-lithium phosphate anode material, improve lithium manganate battery specific capacity at high temperature.
In sum, by synthetic method and the condition of using among the present invention, can prepare easily and fast have good degree of crystallinity, higher purity and excellent multiplying power discharging characteristic and the novel anode material of high-temperature cycle.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the invention, the accompanying drawing of required use was done to introduce simply during the below will describe embodiment, apparently, accompanying drawing relevant of the present invention in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the X-ray diffractogram of the sample of acquisition among comparative example 1 of the present invention and the embodiment 1 ~ 4;
Fig. 2 is the cycle characteristics figure of sample under the room temperature different multiplying that obtains among comparative example 2 of the present invention and the embodiment 5 ~ 8;
Fig. 3 is the first charge-discharge curve chart of the sample of acquisition among comparative example 3 of the present invention and the embodiment 9 ~ 12, and wherein up curve and descending curve from left to right represent embodiment 12, comparative example 3, embodiment 11, embodiment 10 and embodiment 9 all successively;
Fig. 4 is the cycle characteristics figure of sample under the room temperature different multiplying that obtains among comparative example 4 of the present invention and the embodiment 13.
Embodiment
The invention discloses a kind of lithium ion secondary battery anode material, use general formula xLiMnPO
4/ (1-x) LiMn
2O
4Expression is by LiMnPO
4Film coated LiMn
2O
4, 0≤x≤0.1 wherein.
The present invention also provides a kind of method for preparing above-mentioned lithium ion secondary battery anode material, specifically comprises the steps:
Take by weighing water-soluble Li source compound, water-soluble manganese source compound, ammonium phosphate salt and citric acid according to mol ratio Li:Mn:P: citric acid=3:1:1:1, add distilled water mixing wiring solution-forming, add the LiMn of stoichiometric proportion
2O
4Magnetic agitation 3 ~ 5h, be transferred in the hydro-thermal inner bag of polytetrafluoroethylene, add water to 70 ~ 80vol% of inner bag, put into stainless steel cauldron, place 180 ~ 200 ℃ vacuum drying oven to react 8 ~ 12h, naturally cool to room temperature, after carrying out repeatedly centrifugation and washing, with 100 ~ 120 ℃ of lower dry 10 ~ 12h of products therefrom, grinding namely obtains LiMnPO after taking out
4Coat LiMn
2O
4Positive electrode.
Described water-soluble manganese source compound is selected from manganese acetate, manganese nitrate, manganese chloride or manganese sulfate; Described water-soluble Li source compound is selected from lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate; Described ammonium phosphate salt is ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
Among the following embodiment, described water-soluble manganese source compound is manganese acetate; Described water-soluble Li source compound is lithium hydroxide.
Further, the invention provides a kind of lithium ion secondary battery positive electrode, comprise matrix and the coating material that places matrix surface, described coating material comprises: above-mentioned positive electrode, electric conducting material and bonding agent.
Matrix can adopt material well known to those skilled in the art in the above-mentioned lithium ion secondary battery positive electrode, such as aluminium foil; Electric conducting material is preferably conductive black super P in the coating material; Bonding agent can be polytetrafluoroethylene, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate or butadiene-styrene rubber.
Lithium ion secondary battery positive electrode provided by the invention can adopt following method preparation:
Make positive plate on the matrix with being dissolved in 1-METHYLPYRROLIDONE (NMP) and being pressed in after above-mentioned lithium ion secondary battery anode material, electric conducting material, the binding agent mixing.
Further, the present invention also provides a kind of lithium rechargeable battery, comprising: above-mentioned lithium ion secondary battery positive electrode, negative pole, be arranged on barrier film and electrolyte between positive pole and the negative pole.
The present invention does not have particular restriction to described Separator for Lithium-ion battery, considers from cost factor, is preferably polyethylene barrier film or polypropylene diaphragm.
The present invention does not have particular restriction to described electrolyte of lithium-ion secondary battery, can be for well known to a person skilled in the art the nonaqueous electrolytic solution for serondary lithium battery, as contain LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiCH
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAlCl
4, LiSiF
6, LiB (C
6H
5)
4, one or more the electrolytical nonaqueous electrolytic solutions among LiCl and the LiBr, be preferably LiPF
6Nonaqueous electrolytic solution.
The general formula of the present invention's preparation is xLiMnPO
4/ (1-x) LiMn
2O
4Lithium ion secondary battery anode material can be used as the positive electrode of column lithium ion battery, rectangular lithium ion battery and button-shaped lithium ion battery, and can be used as the positive electrode of lithium-ion-power cell and lithium-ion energy storage battery.
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is described in detail, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, the every other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work belongs to the scope of protection of the invention.
Comparative example 1
Directly adopt business-like LiMn
2O
4
With LiOHH
2O, Mn (CH
3COO)
24H
2O, NH
4H
2PO
4Take by weighing synthetic LiMnPO with citric acid according to mol ratio 3:1: 1:1
4Raw material, add a certain amount of distilled water and dissolved, with LiMnPO
4: LiMn
2O
4Mass ratio is 0.01:1 weighing LiMn
2O
4, with described solution magnetic agitation 3h, then, be transferred in the hydro-thermal inner bag of 100mL polytetrafluoroethylene, add water to the 70vol% of inner bag, put into stainless steel cauldron, as for vacuum drying oven, under 180 ℃ condition, react 12h, at last, when reactor naturally cools to room temperature, after carrying out repeatedly centrifugation and washing, with 100 ℃ of lower dry 12h of products therefrom, grinding namely obtains 1wt%LiMnPO after taking out
4The LiMn that coats
2O
4Positive electrode.
Embodiment 2
With LiOHH
2O, Mn (CH
3COO)
24H
2O, NH
4H
2PO
4Take by weighing synthetic LiMnPO with citric acid according to mol ratio 3:1: 1:1
4Raw material, add a certain amount of distilled water and dissolved, with LiMnPO
4: LiMn
2O
4Mass ratio is 0.03:1 weighing LiMn
2O
4, with described solution magnetic agitation 4h, then, be transferred in the hydro-thermal inner bag of 100mL polytetrafluoroethylene, add water to the 75vol% of inner bag, put into stainless steel cauldron, as for vacuum drying oven, under 190 ℃ condition, react 10h, at last, when reactor naturally cools to room temperature, after carrying out repeatedly centrifugation and washing, with 110 ℃ of lower dry 11h of products therefrom, grinding namely obtains 3wt%LiMnPO after taking out
4The LiMn that coats
2O
4Positive electrode.
Embodiment 3
With LiOHH
2O, Mn (CH
3COO)
24H
2O, NH
4H
2PO
4Take by weighing synthetic LiMnPO with citric acid according to mol ratio 3:1: 1:1
4Raw material, add a certain amount of distilled water and dissolved, with LiMnPO
4: LiMn
2O
4Mass ratio is 0.05:1 weighing LiMn
2O
4, with described solution magnetic agitation 5h, then, be transferred in the hydro-thermal inner bag of 100mL polytetrafluoroethylene, add water to the 80vol% of inner bag, put into stainless steel cauldron, as for vacuum drying oven, under 200 ℃ condition, react 8h, at last, when reactor naturally cools to room temperature, after carrying out repeatedly centrifugation and washing, with 120 ℃ of lower dry 10h of products therefrom, grinding namely obtains 5wt%LiMnPO after taking out
4The LiMn that coats
2O
4Positive electrode.
Embodiment 4
With LiOHH
2O, Mn (CH
3COO)
24H
2O, NH
4H
2PO
4Take by weighing synthetic LiMnPO with citric acid according to mol ratio 3:1: 1:1
4Raw material, add a certain amount of distilled water and dissolved, with LiMnPO
4: LiMn
2O
4Mass ratio is 0.1:1 weighing LiMn
2O
4, with described solution magnetic agitation 4h, then, be transferred in the hydro-thermal inner bag of 100mL polytetrafluoroethylene, add water to the 80vol% of inner bag, put into stainless steel cauldron, as for vacuum drying oven, under 200 ℃ condition, react 10h, at last, when reactor naturally cools to room temperature, after carrying out repeatedly centrifugation and washing, with 120 ℃ of lower dry 12h of products therefrom, grinding namely obtains 10wt%LiMnPO after taking out
4The LiMn that coats
2O
4Positive electrode.
As can be seen from Figure 1, no matter be comparative example 1, or embodiment 1 ~ 4, the sample that the experiment route that designs according to us obtains, in their X ray diffracting spectrums, all do not see the existence of impurity peaks, show very high purity, and through after coating processing, not only do not change the peak position of diffraction maximum, and lattice constant is substantially unchanged.
Comparative example 2
LiMn with comparative example 1
2O
4Mix in the 8:1:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature (25 ℃).
1wt%LiMnPO with embodiment 1 preparation
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature (25 ℃).
Embodiment 6
3.0wt%LiMnPO with embodiment 2 preparations
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature (25 ℃).
Embodiment 7
5wt%LiMnPO with embodiment 3 preparations
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature (25 ℃).
Embodiment 8
10wt%LiMnPO with embodiment 4 preparations
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature (25 ℃).
As can be seen from Figure 2, the sample that obtains by comparative example 2, embodiment 5, embodiment 6, embodiment 7 and embodiment 8 at room temperature capacity does not all have significantly decay.After comparative example 2 circulates through 50 times, its specific discharge capacity drops to the every gram of 100.7 Milliampere Hours from the initial every gram of 105.2 Milliampere Hours, capability retention is about 95%, and the sample that obtains by embodiment 5, embodiment 6, embodiment 7 and embodiment 8, they are after circulating through 50 times, its specific discharge capacity is respectively the every gram of 102.7 Milliampere Hours, the every gram of 96 Milliampere Hours, the every gram of 83.6 Milliampere Hours and the every gram of 74.6 Milliampere Hours, and capability retention is respectively 94%, 99%, 100% and 100%.
Comparative example 3
LiMn with comparative example 1
2O
4Mix in the 8:1:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is high temperature (55 ℃).
Embodiment 9
1wt%LiMnPO with embodiment 1 preparation
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, and is dissolved in the 1-METHYLPYRROLIDONE (NMP), is coated in after stirring and makes positive plate on the aluminium foil.Described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is high temperature (55 ℃).
3.0wt%LiMnPO with embodiment 2 preparations
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is high temperature (55 ℃).
Embodiment 11
5wt%LiMnPO with embodiment 3 preparations
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is high temperature (55 ℃).
Embodiment 12
10wt%LiMnPO with embodiment 4 preparations
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 200 milliamperes of every grams (1C), and discharging current is 200 milliamperes of every grams (1C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is high temperature (55 ℃).
As seen from Figure 3, at high temperature, except the sample that embodiment 12 obtains, the first discharge specific capacity of the sample that other embodiment obtain all will be higher than the specific discharge capacity that comparative example 3 obtains sample.Can find out that from form 1 comparative example 3 obtains its capacity attenuation of sample or apparent in view.After 50 circulations, its specific capacity drops to the every gram of less than 75 Milliampere Hours from the initial every gram of 89 Milliampere Hours, capability retention is about 84%, and the sample that obtains by embodiment 9, embodiment 10 and embodiment 11, they are after circulating through 50 times, its specific capacity is respectively the every gram of 115 Milliampere Hours, the every gram of 106 Milliampere Hours and the every gram of 95 Milliampere Hours, and capability retention is respectively 97%, 98% and 91%.
Table 1 comparative example 3 and embodiment 9 ~ 12 obtain sample capability retention at high temperature
Comparative example 4
LiMn with comparative example 1
2O
4Mix in the 8:1:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 20 milliamperes of every grams (0.1C), discharging current is respectively 20 milliamperes of every grams (0.1C), 40 milliamperes of every grams (0.2C), 100 milliamperes of every grams (0.5C), 200 milliamperes of every grams (1C), 400 milliamperes of every grams (2C), 1000 milliamperes of every grams (5C) and 2000 milliamperes of every grams (10C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature (25 ℃).
Embodiment 13
1wt%LiMnPO with embodiment 1 preparation
4The LiMn that coats
2O
4With conductive black super P, binding agent PVDF in 8:1: 1 ratio is mixed, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 110 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 20 milliamperes of every grams (0.1C), discharging current is respectively 20 milliamperes of every grams (0.1C), 40 milliamperes of every grams (0.2C), 100 milliamperes of every grams (0.5C), 200 milliamperes of every grams (1C), 400 milliamperes of every grams (2C), 1000 milliamperes of every grams (5C) and 2000 milliamperes of every grams (10C), and the charging/discharging voltage interval is between 3.3 ~ 4.3 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature (25 ℃).
As can be seen from Figure 4, sample by comparative example 4 acquisitions; little multiplying power discharging (0.1C) specific capacity is the every grams of 122.5 Milliampere Hours; but when large multiplying power discharging (5C); specific capacity is the every grams of 74.3 Milliampere Hours, and its capability retention is 60%, when at large multiplying power discharging (10C); specific capacity only is the every gram of 54.3 Milliampere Hours, and its capability retention is 44%.And pass through the sample that embodiment 13 obtains, and little multiplying power discharging (0.1C) specific capacity is the every grams of 113.9 Milliampere Hours, and when at large multiplying power discharging (5C), specific capacity is the every grams of 88.2 Milliampere Hours, and its capability retention is 78%, has showed preferably high rate performance.
Can say, utilize comparatively cheapness, environmental protection, have the LiMnPO of olivine structural
4Coat LiMn
2O
4Positive electrode not only helps to fall the cost of ground material, can also effectively improve high temperature cyclic performance and the multiplying power property of positive electrode, so this system material is a kind of novel high-performance positive electrode.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that does not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other concrete form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in the scope.Any Reference numeral in the claim should be considered as limit related claim.
In addition, be to be understood that, although this specification is described according to execution mode, but be not that each execution mode only comprises an independently technical scheme, this narrating mode of specification only is for clarity sake, those skilled in the art should make specification as a whole, and the technical scheme among each embodiment also can through appropriate combination, form other execution modes that it will be appreciated by those skilled in the art that.
Claims (6)
1. a lithium ion secondary battery anode material is characterized in that: use general formula xLiMnPO
4/ (1-x) LiMn
2O
4Expression is by LiMnPO
4Film coated LiMn
2O
4, 0≤x≤0.1 wherein.
2. the preparation method of the described lithium ion secondary battery anode material of claim 1 is characterized in that, comprises the steps:
Take by weighing water-soluble Li source compound, water-soluble manganese source compound, ammonium phosphate salt and citric acid according to mol ratio Li:Mn:P: citric acid=3:1:1:1, add distilled water mixing wiring solution-forming, add the LiMn of stoichiometric proportion
2O
4Magnetic agitation 3 ~ 5h, be transferred in the hydro-thermal inner bag of polytetrafluoroethylene, add water to 70 ~ 80vol% of inner bag, put into stainless steel cauldron, place 180 ~ 200 ℃ vacuum drying oven to react 8 ~ 12h, naturally cool to room temperature, after carrying out repeatedly centrifugation and washing, with 100 ~ 120 ℃ of lower dry 10 ~ 12h of products therefrom, grinding namely obtains LiMnPO after taking out
4Coat LiMn
2O
4Positive electrode.
3. preparation method according to claim 2, it is characterized in that: described water-soluble manganese source compound is selected from manganese acetate, manganese nitrate, manganese chloride or manganese sulfate; Described water-soluble Li source compound is selected from lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate; Described ammonium phosphate salt is ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
4. preparation method according to claim 3, it is characterized in that: described water-soluble manganese source compound is manganese acetate; Described water-soluble Li source compound is lithium hydroxide.
5. a lithium ion secondary battery positive electrode comprises matrix and the coating material that places matrix surface, and it is characterized in that: described coating material comprises lithium ion secondary battery anode material claimed in claim 1, electric conducting material and bonding agent.
6. a lithium rechargeable battery is characterized in that, comprising: lithium ion secondary battery positive electrode claimed in claim 5, negative pole, be arranged on barrier film and electrolyte between positive pole and the negative pole.
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